Diblock Copolymers Prepared by Cross Metathesis

ABSTRACT

This invention relates to a composition comprising a multiblock polyolefin represented by the formula: PO—C(R 11 )(R 12 )—C(R 13 )═C(R 14 )—C(R 15 )(R 16 )—PO*, or isomers thereof, wherein R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 , are each independently a substituted or unsubstituted C 1  through C 4  hydrocarbyl group or a hydrogen; PO and PO* are polyolefins; PO and PO* are each independently a substituted or unsubstituted hydrocarbyl group having 9 to 4000 carbon atoms, provided that at least one of PO and PO* are C 20  or greater, said polyolefin having: 1) an internal unsaturation as shown by the  13 C NMR peak at between about 128 and about 132 ppm; 2) an Mn ratio “Z”=0.1 to 10 where Z is the Mn (as determined by  13 C NMR) divided by Mn (as determined according to Gel Permeation Chromotography using polystyrene standards); and 3) optionally, from 0.3(J) and 0.75(J) internal unsaturations per 1000 carbons as determined by  1 H NMR spectroscopy, where J is the number of reactive groups per 1000 carbons for the mixture of vinyl terminated polyolefins that become PO and PO*, before they are coupled by an alkene metathesis catalyst.

RELATED APPLICATIONS

This application is related to U.S. Ser. No. 12/143,663, filed on Jun.20, 2008 (Published as WO 2009/155471); U.S. Ser. No. 12/487,739, filedon Jun. 19, 2009 (Published as WO 2009/155472); U.S. Ser. No.12/488,066, filed on Jun. 19, 2009 (Published as WO 2009/155510); Ser.No. 12/488,093, filed on Jun. 19, 2009 (Published as WO 2009/155517);and U.S. Ser. No. 12/642,453, filed Dec. 18, 2009; which is acontinuation-in-part application of U.S. Ser. No. 12/533,465 filed onJul. 31, 2009, which claims priority to and the benefit of U.S. Ser. No.61/136,172, filed on Aug. 15, 2008; which are all incorporated byreference herein.

This invention also relates to the following concurrently filedapplications:

a) Attorney Docket Number 2011EM011, entitled “Novel Catalysts andMethods of use Thereof to Produce Vinyl Terminated Polymers”;

b) Attorney Docket Number 2011EM012, entitled “Amine FunctionalizedPolyolefin and Methods for Preparation Thereof”;

c) Attorney Docket Number 2011EM013, entitled “Enhanced CatalystPerformance for Production of Vinyl Terminated Propylene andEthylene/Propylene Macromers”;

d) Attorney Docket Number 2011EM015, entitled “Amphiphilic BlockPolymers Prepared by Alkene Metathesis”;

e) Attorney Docket Number 2011EM016, entitled “Vinyl Terminated HigherOlefin Polymers and Methods to Produce Thereof”;

f) Attorney Docket Number 2011EM017, entitled “Hydrosilylation of VinylTerminated Macromers with Metallocenes”;

g) Attorney Docket Number 2011EM018, entitled “Olefin Triblock Polymersvia Ring-Opening Metathesis Polymerization”;

h) Attorney Docket Number 2011EM019, entitled “Block Copolymers fromSilylated Vinyl Terminated Macromers”; and

i) Attorney Docket Number 2011EM020, entitled “Vinyl Terminated HigherOlefin Copolymers and Methods to Produce Thereof”; and

j) Attorney Docket Number 2011EM034, entitled “Branched Vinyl Terminated

Polymers and Methods for Production Thereof”.

FIELD OF THE INVENTION

This invention relates to metathesis preparation of multiblock polymersfrom vinyl-terminated polyolefins.

BACKGROUND OF THE INVENTION

Metathesis is generally thought of as the interchange of radicalsbetween two compounds during a chemical reaction. There are severalvarieties of metathesis reactions, such as ring opening metathesis,acyclic diene metathesis, ring closing metathesis and cross metathesis.These reactions, however, have had limited success with the metathesisof functionalized olefins.

Methods for the production of polyolefins with end-functionalized groupsare typically multi-step processes that often create unwantedby-products and waste of reactants and energy.

R. T. Mathers and G. W. Coates Chem. Commun., 2004, pp. 422-423 discloseexamples of using cross-metathesis to functionalize polyolefinscontaining pendant vinyl groups to form polar-functionalized productswith a graft-type structure.

D. Astruc et al. J. Am. Chem. Soc. 2008, 130, pp. 1495-1506, and D.Astruc et al. Angew. Chem. Int. Ed., 2005, 44, pp. 7399-7404 discloseexamples of using cross metathesis to functionalize non-polymericmolecules containing vinyl groups.

For reviews of methods to form end-functionalized polyolefins, see: (a)S. B. Amin and T. J. Marks Angew. Chem. Int. Ed., 2008, 47, pp.2006-2025; (b) T. C. Chung Prog. Polym. Sci., 2002, 27, pp. 39-85; (c)R. G. Lopez, F. D'Agosto, C. Boisson Prog. Polym. Sci., 2007, 32, pp.419-454.

U.S. Ser. No. 12/487,739, filed Jun. 19, 2009 discloses certain vinylterminated oligomers and polymers that are functionalized for use inlubricant applications.

U.S. Ser. No. 12/143,663, filed on Jun. 20, 2008 discloses certain vinylterminated oligomers and polymers that are functionalized in U.S. Ser.No. 12/487,739, filed Jun. 19, 2009.

U.S. Ser. No. 12/488,093, filed Jun. 19, 2009 discloses endfunctionalized polyolefins prepared from vinyl terminated polyolefins bycross metathesis.

Additional references of interest include U.S. Pat. No. 4,988,764 andU.S. Pat. No. 6,225,432.

Thus, metathesis reactions can provide functionalized polyolefins thathave end-functionalization. However, to date it has not been feasible topolymerize polyolefins having end-functionalization to each other.

Thus a need exists for a method to prepare polyolefins that utilizeend-functionalization to provide new polymers with unique physicalproperties.

Diblock polymers prepared by metathesis from vinyl-terminatedpolyolefins feature a chemically reactive internal site of unsaturationand are of interest for use in a broad range of applications ascompatibilizers, tie-layer modifiers, surfactants, and surfacemodifiers, among other things. Hydrogenation leads to unique diblockpolymers that can be used in applications such as compatibilizers,tie-layer modifiers, surfactants, and surface modifiers, among otherthings. Herein is described a novel method for their production by themetathesis of vinyl-terminated polyolefins. This method is useful in arange of polyolefins, including isotactic polypropylene (iPP), atacticpolypropylene (aPP), ethylene propylene copolymer (EP), and polyethylene(PE).

SUMMARY OF THE INVENTION

This invention relates to a composition comprising a multiblockpolyolefin represented by the formula (X):

PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X),

or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each, independently, asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen;PO and PO* are each, independently, polyolefins, preferably derived fromvinyl terminated polyolefins, preferably PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms, provided that at least one of PO and PO* are C₂₀or greater, said multiblock polyolefin having:

1) an internal unsaturation as shown by the ¹³C NMR peak at betweenabout 128 and about 132 ppm;

2) an Mn ratio “Z”=0.1 to 10, where Z is the Mn (as determined by ¹³CNMR) divided by Mn (as determined according to Gel PermeationChromotography using polystyrene standards); and

3) optionally, from 0.3 (J) and 0.75(J) internal unsaturations per 1000carbons as determined by ¹H NMR spectroscopy, where J is the number ofallyl chain ends per 1000 carbons for the mixture of vinyl terminatedpolyolefins, that preferably become PO and PO*, before they are coupledby an alkene metathesis catalyst.

This invention also relates to a process to prepare a compositioncomprising a multiblock polyolefin represented by the formula (X):

PO—C(R¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X),

or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen;PO and PO* are each, independently, polyolefins, preferably derived fromvinyl terminated polyolefins, preferably PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms, provided that at least one of PO and PO* are C₂₀or greater, said multiblock polyolefin having:

1) an internal unsaturation as shown by the ¹³C NMR peak at betweenabout 128 and about 132 ppm, (alternately the multiblock polyolefin has0.10 to 35 internal unsaturations per 1,000 carbon atoms, preferably 0.2to 20, preferably 0.3 to 10, as determined by ¹³C NMR);

2) an Mn ratio “Z”=0.1 to 10, where Z is the Mn (as determined by ¹³CNMR) divided by Mn (as determined according to Gel PermeationChromotography using polystyrene standards); and

3) optionally, from 0.3(J) and 0.75(J) internal unsaturations per 1000carbons as determined by ¹H NMR spectroscopy, where J is the number ofreactive groups per 1000 carbons for the mixture of vinyl terminatedpolyolefins, that preferably become PO and PO*, before they are coupledby an alkene metathesis catalyst.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a ¹H NMR decoupled ¹³C NMR spectrum of the homocoupled productof 1-octadecene (top) and the unsaturated region expanded and magnified(bottom).

FIG. 2 is a ¹H NMR decoupled ¹³C NMR spectrum of product fromhomometathesis of a vinyl-terminated atactic polypropylene (M_(n) 421)(top) and an expansion of the unsaturated region (bottom).

FIG. 3 is a ¹³C NMR spectra of cross metathesis product of 1-octadeceneand vinyl-terminated aPP (top) and the unsaturated region expanded(bottom).

FIG. 4 is a stacked plot of the saturated region of the heterocoupledproduct of cross-metathesis products from 1-octadecene andvintyl-terminated aPP, i.e., a ¹³C NMR spectra of aliphatic Region ofCoupling Products. Top: Homometathesis of 1-octadecene, Middle:Homometathesis of vinyl-terminated aPP, Bottom: Cross-metathesisreaction of 1-octadecene and vinyl-terminated aPP.

DETAILED DESCRIPTION

The term “polyolefin” as used herein means an oligomer or polymer of twoor more olefin mer units and specifically includes oligomers andpolymers as defined below. An “olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon andhydrogen having at least one double bond.

A propylene polymer or oligomer contains at least 50 mol % of propylene,an ethylene polymer or oligomer contains at least 50 mole % of ethylene,and so on.

For purposes of this specification and the claims appended thereto, whena polymer or copolymer is referred to as comprising an olefin,including, but not limited to ethylene, propylene, and butene, theolefin present in such polymer or copolymer is the polymerized form ofthe olefin. For example, when a copolymer is said to have an “ethylene”content of 35 wt % to 55 wt %, it is understood that the mer unit in thecopolymer is derived from ethylene in the polymerization reaction andsaid derived units are present at 35 wt % to 55 wt %, based upon theweight of the copolymer. A “polymer” has two or more of the same ordifferent mer units. A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. The term “different”as used to refer to mer units indicates that the mer units differ fromeach other by at least one atom or are different isomerically.Accordingly, the definition of copolymer, as used herein, includesterpolymers and the like. An oligomer is typically a polymer having alow molecular weight (such an Mn of less than 25,000 g/mol, preferablyless than 2,500 g/mol) or a low number of mer units (such as 75 merunits or less).

As used herein, Mn is number average molecular weight (measured by ¹HNMR unless stated otherwise), Mw is weight average molecular weight(measured by Gel Permeation Chromatography), and Mz is z averagemolecular weight (measured by Gel Permeation Chromatography), wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD) is defined to be Mw (measured by Gel Permeation Chromatography)divided by Mn (measured by ¹H NMR). Unless otherwise noted, allmolecular weight units (e.g., Mw, Mn, Mz) are g/mol.

“Allyl chain ends” (also referred to as “vinyl termination”, “vinylchain ends” “allylic vinyl end group” or “vinyl content”) is defined tobe a polyolefin (oligomer or polymer) having at least one terminusrepresented by formula I:

where the “••••” represents the polyolefin chain. In a preferredembodiment the allyl chain end is represented by the formula II:

The amount of allyl chain ends is determined using ¹H NMR at 120° C.using deuterated tetrachloroethane as the solvent on a 500 MHz machineand in selected cases confirmed by ¹³C NMR. Resconi has reported protonand carbon assignments (neat perdeuterated tetrachloroethane used forproton spectra while a 50:50 mixture of normal and perdeuteratedtetrachloroethane was used for carbon spectra; all spectra were recordedat 100° C. on a Bruker AM 300 spectrometer operating at 300 MHz forproton and 75.43 MHz for carbon) for vinyl terminated propyleneoligomers in J American Chemical Soc., 114, 1992, pp. 1025-1032 that areuseful herein.

“Isobutyl chain end”, also referred to as an “isobutyl end group” isdefined to be a polyolefin (oligomer or polymer) having at least oneterminus represented by the formula:

where M represents the polyolefin (oligomer or polymer) chain. In apreferred embodiment, the isobutyl chain end is represented by one ofthe following formulae:

where M represents the polyolefin chain.

The percentage of isobutyl end groups is determined using ¹³C NMR (asdescribed in the example section) and the chemical shift assignments inResconi et al, J. Am. Chem. Soc., 1992, 114, pp. 1025-1032 for 100%propylene oligomers (and polymers) and set forth in FIG. 2 of WO2009/155471 for E-P oligomers (and polymers).

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallylic vinyl groups.

Unless otherwise indicated, the term “internal unsaturation” means adouble bond that is not an allyl chain end as defined above, a vinylene,or vinylidene unsaturation.

The term “diblock” is defined to mean that there are at least twopolyolefin different portions in the multiblock polyolefin, e.g., PO andPO* are different. The term “different” as used to refer to polyolefinsindicates that the mer units of the polyolefins differ from each otherby at least one atom, the mer units of the polyolefins differisomerically, or the polyolefins differ in Mn, Mw, Mz, tacticity, Mw/Mn,g′vis, vinyl, vinylidene, vinylene, or internal unsaturation content,amount of comonomer (when the comonomer is the same or different in thepolyolefins), density (ASTM D 1505), melting point, heat of fusion,Brookfield viscosity, specific gravity (ASTM D 4052), or any other fluidor polyolefin property described in US 2008/0045638, paragraphs [0593]to [0636](in event of conflict between test procedures in the instantspecification and US 2008/0045638, the instant specification shallcontrol). The term “multiblock” is defined to mean more than onepolyolefin portion is present in the multiblock polyolefin. The term“vinyl terminated polyolefin” also referred to as “vinyl terminatedmacromer” or “VTM” is defined to be a polyolefin (oligomer or polymer)having at least 30% allyl chain ends (relative to total unsaturation),preferably having an Mn of at least 300 g/mol, preferably from 500 to100,000 g/mol.

As used herein, the new notation for the Periodic Table Groups is usedas described in Chemical and Engineering News, 63(5), 27 (1985).

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom or a heteroatom containing group.For example methyl cyclopentadiene (Cp) is a Cp group substituted with amethyl group and ethyl alcohol is an ethyl group substituted with an —OHgroup.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁ to C₂₀ radicals, that may be linear, branched, orcyclic (aromatic or non-aromatic); and include substituted hydrocarbylradicals as defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with a heteroatom or heteroatomcontaining group, preferably with at least one functional group such ashalogen (Cl, Br, I, F), NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least oneheteroatom has been inserted within the hydrocarbyl radical, such ashalogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂,GeR*₂, SnR*₂, PbR*₂, and the like, where R* is, independently, hydrogenor a hydrocarbyl.

A “substituted alkyl” or “substituted aryl” group is an alkyl or arylradical made of carbon and hydrogen where at least one hydrogen isreplaced by a heteroatom, a heteroatom containing group, or a linear,branched, or cyclic substituted or unsubstituted hydrocarbyl grouphaving 1 to 30 carbon atoms.

By “reactive termini” is meant a polymer having a vinyl, vinylidene,vinylene or other terminal group that can be polymerized into a growingpolymer chain.

Bromine number is determined by ASTM D 1159. ICPES (Inductively CoupledPlasma Emission Spectrometry), which is described in J. W. Olesik,“Inductively Coupled Plasma-Optical Emission Spectroscopy,” in theEncyclopedia of Materials Characterization, C. R. Brundle, C. A. Evans,Jr. and S. Wilson, Eds., Butterworth-Heinemann, Boston, Mass., 1992, pp.633-644, is used to determine the amount of an element in a material.

This invention relates to a composition comprising a multiblockpolyolefin represented by the formula (X):

PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X),

or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen;PO and PO* are each, independently, polyolefins, preferably derived fromvinyl terminated polyolefins, preferably PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms, provided that at least one of PO and PO* are C₂₀or greater, said multiblock polyolefin having:

1) an internal unsaturation as shown by the ¹³C NMR peak at betweenabout 128 and about 132 ppm;

2) an Mn ratio “Z”=0.1 to 10, preferably 0.25 to 4, preferably 0.5 to 2,preferably 0.75 to 1.5, where Z is the Mn (as determined by ¹³C NMR)divided by Mn (as determined according to Gel Permeation Chromotographyusing polystyrene standards); and

3) optionally, from 0.30 (J) and 0.75 (J) (preferably from 0.35 (J) and0.70 (J), preferably from 0.40 (J) and 0.60 (J)) internal unsaturationsper 1000 carbons as determined by ¹H NMR spectroscopy, where J is thenumber of reactive groups per 1000 carbons for the mixture of vinylterminated polyolefins, that preferably become PO and PO*, before theyare coupled by an alkene metathesis catalyst.

A preferred embodiment for the multiblock polyolefin of formula (X) hasPO and PO* being different. An example of this would be having PO beingisotactic PP and PO* being an EP copolymer, with the ethylene content inthe PO* being about 50% by weight. A preferred embodiment for themultiblock polyolefin of formula (X) has PO and PO* being different,with PO being immiscible with PO*. By immiscible is meant that if thevinyl terminated polyolefins that became PO and PO* were blendedtogether they would form a heterogeneous composition.

By homogeneous composition it is meant a composition havingsubstantially one morphological phase. (A co-continuous morphology isconsidered a single state for purposes of this invention and the claimsthereto.) For example, a blend of two polymers where one polymer ismiscible with another polymer is said to be homogeneous in the solidstate. Such morphology is determined using optical microscopy, scanningelectron microscopy (SEM) or atomic force microscopy (AFM), in the eventthe optical microscopy, SEM and AFM provide different data, then the SEMdata shall be used. By contrast, two separate phases would be observedfor an immiscible blend. A miscible blend is homogeneous, while animmiscible blend is heterogeneous.

In a preferred embodiment, PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, differ in comonomer contentpreferably by at least 5 mol %, relative to each other, preferably by atleast 10 mol % different, preferably by at least 20 mol % different,preferably by at least 30 mol % different, preferably by at least 40 mol% (for example, an ethylene copolymer having 20 mol % propylene differsfrom a propylene copolymer having 5 mol % butene by 15 mol %). In apreferred embodiment, PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, differ in Mn, Mw, Mz, Mw/Mn,g′vis, vinyl, vinylidene, vinylene, or internal unsaturation content,density (ASTM D-1505), melting point, heat of fusion, % tacticity,and/or crystallization point by at least 5% relative to each other,preferably by at least 10 mol % different, preferably by at least 20 mol% different, preferably by at least 30 mol % different, preferably by atleast 40 mol % (for example, an a polymer having an Mw of 500 g/moldiffers from a polymer having an Mw of 732 by 46%). In a preferredembodiment, the Tm's, according to the DSC, of PO and PO*, and/or thevinyl terminated polyolefins PO and PO* are derived from, are differentby at least 5° C., preferably by at least 10° C., preferably by at least20° C., preferably by at least 30° C., preferably by at least 40° C.,preferably by at least 50° C., preferably by at least 60° C., preferablyby at least 70° C., preferably by at least 80° C. Likewise, in apreferred embodiment, the crystallization temperatures (Tc), accordingto the DSC, of PO and PO*, and/or the vinyl terminated polyolefins POand PO* are derived from, are different by at least 5° C., preferably byat least 10° C., preferably by at least 20° C., preferably by at least30° C., preferably by at least 40° C., preferably by at least 50° C.,preferably by at least 60° C., preferably by at least 70° C., preferablyby at least 80° C. Further, in a preferred embodiment, the heat offusion (Hf), determined by DSC, of PO and PO*, and/or the vinylterminated polyolefins PO and PO* are derived from, are at least 5 J/gdifferent, preferably at least 10 J/g different, preferably at least 20J/g different, preferably at least 50 J/g different, preferably at least80 J/g different.

In a preferred embodiment, the multiblock polyolefin composition (i.e.,the multiblock polyolefin and any unreacted starting materials, prior tofractionation or washing), has little or no reactive termini as shown bya ratio of 2.0 or greater (preferably 5 or greater, preferably 10 orgreater, preferably 20 or greater) for the intensity of the internalunsaturation peaks at about 128 to 132 ppm to the reactive termini peaksat about 114 and 139 ppm in the ¹³C NMR spectrum.

In certain embodiments, the multiblock polymer has an average of about0.75 to about 1.25 internal unsaturation sites per polyolefin chain, asdetermined by ¹H NMR of the polyolefin for multiblock polymers having anMn of up to 60,000 g/mol as determined by ¹H NMR.

In a preferred embodiment, PO* is PO and/or PO is PO*. In anotherpreferred embodiment, the multiblock polyolefin is a mixture of (a)PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*; (b)PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO; and (c)PO*—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*. Preferably, the mixturecomprises about 30% to about 70% of (a)PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*, about 1% to about 30% of(b) PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO and about 1% to about30% (c) PO*—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*.

In a preferred embodiment, the various components of the multiblockpolyolefin can be separated from each other (e.g., (a) can be separatedfrom (b) and (c)) using the preparative TREF procedure below. In apreferred embodiment, once the multiblock polyolefin has beenfractionated, the fraction containing the largest mass is selected (andis presumed to be the multiblock polyolefin produced herein) andsubjected to characterization, such as DSC (as described below).Preferably, the multiblock polyolefin (e.g., the selected fraction withthe largest mass) shows two peak melting temperatures (Tm) according tothe DSC and the Tm's are different by at least 5° C., preferably by atleast 10° C., preferably by at least 20° C., preferably by at least 30°C., preferably by at least 40° C., preferably by at least 50° C.,preferably by at least 60° C., preferably by at least 70° C., preferablyby at least 80° C. Likewise, preferably the multiblock polyolefin (e.g.,the selected fraction with the largest mass) shows two crystallizationtemperatures (Tc) according to the DSC and the Tc's are different by atleast 5° C., preferably by at least 10° C., preferably by at least 20°C., preferably by at least 30° C., preferably by at least 40° C.,preferably by at least 50° C., preferably by at least 60° C., preferablyby at least 70° C., preferably by at least 80° C. Further, in apreferred embodiment, the heat of fusion (Hf), determined by DSC, of themultiblock polyolefin (e.g., the selected fraction with the largestmass) is between the Hf's of the starting vinyl terminated polyolefins.Preferably, the Hf of the multiblock polyolefin (e.g., the selectedfraction with the largest mass) is at least 5 J/g different than the Hfof the starting vinyl terminated polyolefin having the highest Hf,preferably at least 10 J/g different, preferably at least 20 J/gdifferent, preferably at least 50 J/g different, preferably at least 80J/g different. In a preferred embodiment, the Hf of the multiblockpolyolefin (e.g., the selected fraction with the largest mass) is atleast 5 J/g less than the Hf of the starting vinyl terminated polyolefinhaving the highest Hf, preferably at least 10 J/g less, preferably atleast 20 J/g less, preferably at least 30 J/g less, preferably at least40 J/g less, preferably at least 50 J/g less, preferably at least 60 J/gless, preferably at least 70 J/g less, preferably at least 80 J/g less,preferably at least 90 J/g less.

In another embodiment, the comonomer content of the multiblockpolyolefin (e.g., the selected fraction with the largest mass) is atleast 5 mol % different than the comonomer content of the starting vinylterminated polyolefin having the highest comonomer content, preferablyat least 10 mol % different, preferably at least 20 mol % different,preferably at least 30 mol % different, preferably at least 40 mol %different. In another embodiment, the comonomer content, of themultiblock polyolefin (e.g., the selected fraction with the largestmass) is between the comonomer contents of the starting vinyl terminatedpolyolefins. A homopolymer shall be considered to have 0 mol %comonomer. Comonomer content can be measured by Fourier TransformInfrared Spectroscopy (FTIR) in conjunction with samples collected byGPC as described in Wheeler and Willis, Applied Spectroscopy, 1993, vol.47, pp. 1128-1130.

A commercial preparative TREF instrument (Model MC2, Polymer Char S.A.)is used to fractionate the resin into Chemical Composition Fractions.Approximately 2 g of polymer is placed into a reactor and dissolved in200 mL of xylene, stabilized with 600 ppm of BHT, at 130° C. forapproximately 60 minutes. The mixture is allowed to equilibrate for 45minutes at 90° C., and then cooled to either 30° C. (standard procedure)or 15° C. (cryo procedure) using a cooling rate of 0.1° C./min. Thetemperature of the cooled mixture is increased until it is within thelowest Isolation Temperature Range to be used (see Table 2) and themixture is heated to maintain its temperature within the specified rangefor 20 minutes. The mixture is sequentially filtered through a 75 microncolumn filter and then a 2 micron disk filter using 10 psi to 50 psi ofpressurized nitrogen. The reactor is washed twice with 50 ml of xyleneheated to maintain the temperature of the wash mixture within thedesignated temperature range and held at that temperature for 20 minutesduring each wash cycle. The fractionation process is continued byintroducing fresh xylene (200 mL of xylene, stabilized with 600 ppm ofBHT) into the reactor, increasing the temperature of the mixture untilit reaches the next highest Isolation Temperature Range in the sequenceindicated in Table 2 and heating the mixture to maintain its temperaturewithin the specified range for 20 minutes prior to filtering it asdescribed above. The extraction cycle is sequentially repeated in thismanner until the mixture has been extracted at all Isolation TemperatureRanges shown in Table 2. The extracts are independently precipitatedwith methanol to recover the individual polymer fractions.

TABLE 2 Preparative TREF Fractionation Isolation Temperature RangesChemical Composition Fraction Designation Isolation Temperature CryoProcedure Standard Procedure Range (° C.) 1 —  0 to 15 2 1  15 to 36* 32 36 to 51 4 3 51 to 59 5 4 59 to 65 6 5 65 to 71 7 6 71 to 77 8 7 77 to83 9 8 83 to 87 10 9 87 to 91 11 10  Greater than 91 *The IsolationTemperature Range for the Standard Procedure is 0 to 36° C.

In a preferred embodiment, the multiblock polyolefin has an Mn of from400 to 120,000 g/mol, preferably 1000 to about 60,000 g/mol, preferably10,000 to 45,000 g/mol, preferably from 20,000 to 42,000 g/mol,preferably about 40,000 g/mol, alternately about 20,000 alternatelyabout 1000 g/mol.

In an embodiment, PO is a polypropylene of a Mn of about 300 to about20,000 g/mol or PO is an ethylene/propylene copolymer of a Mn of about300 to about 20,000 g/mol. In a preferred embodiment, at least one ofthe substituted or unsubstituted hydrocarbyl groups of PO and PO*contain from about 2 to about 18 carbon atoms.

The character of the “blocks” (e.g., the PO and PO*) of the multiblockpolyolefin can be confirmed by the following steps: 1. Purifying themultiblock polymer to wash away any unreacted vinyl terminated polymersto other material that is not the multiblock polyolefin. (The methods todo such will necessarily vary depending on the nature of PO and PO*.Selection of such methods is well within the skill of one of ordinaryskill in the art.) 2. Contacting the multiblock polyolefin with an agentto cause cleavage at the internal unsaturation, such as bycrossmetathesis with ethylene, or cleavage with ozone or permanganate(care should be taken to not cause cleavage at sites other than theinternal unsaturation). Selection of such agents is well within theskill of one of ordinary skill in the art. 3. Recovering and separatingthe cleaved materials. (The methods to do such will necessarily varydepending on the nature of PO and PO*. Selection of such methods is wellwithin the skill of one of ordinary skill in the art.) 4. Characterizingthe separated materials.

This invention presumes that PO and PO* are derived from the vinylterminated polyolefins used to make the multiblock polyolefins.

The multiblock polyolefins produced herein may be used in a broad rangeof applications, such as compatibilizers, tie-layer modifiers,surfactants, surface modifiers, lubricants, detergents, flocculants,viscosity modifiers, Viscosity Index modifiers, emulsifiers,de-emulsifiers, dispersants, plasticizers, surfactants for soaps,detergents, fabric softeners, antistatics, oil additives, anti-foggingor wetting additives, adhesion promoters additives for lubricants and/orfuels, and the like.

Process to Produce Multiblock Polyolefins

This invention relates to a process to prepare a composition comprisinga multiblock polyolefin represented by the formula (X):

PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X),

or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen;PO and PO* are each, independently, polyolefins, preferably derived fromvinyl terminated polyolefins, preferably PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms, provided that at least one of PO and PO* are C₂₀or greater, said multiblock polyolefin having:

1) an internal unsaturation as shown by the ¹³C NMR peak at betweenabout 128 and about 132 ppm;

2) an Mn ratio “Z”=0.1 to 10, preferably 0.25 to 4, preferably 0.5 to 2,preferably 0.75 to 1.5, where Z is the Mn (as determined by ¹³C NMR)divided by Mn (as determined according to Gel Permeation Chromotographyusing polystyrene standards); and

3) optionally, from 0.30 (J) and 0.75 (J) (preferably from 0.35 (J) and0.70 (J), preferably from 0.40 (J) and 0.60 (J)) internal unsaturationsper 1000 carbons as determined by ¹H NMR spectroscopy, where J is thenumber of reactive groups per 1000 carbons for the mixture of vinylterminated polyolefins, that preferably become PO and PO*, before theyare coupled by an alkene metathesis catalyst,

said process comprising contacting an alkene metathesis catalyst withtwo or more vinyl terminated polyolefins, each having at least 30% allylchain ends (relative to total unsaturations).

The reactants (including the vinyl terminate polyolefins, such as thevinyl terminated polyolefins that PO and PO* are derived from) aretypically combined in a reaction vessel at a temperature of 20 to 200°C. (preferably 50 to 160° C., preferably 60 to 140° C.) and a pressureof 0 to 1000 MPa (preferably 0.5 to 500 MPa, preferably 1 to 250 MPa)for a residence time of 0.5 seconds to 10 hours (preferably 1 second to5 hours, preferably 1 minute to 1 hour).

Typically, 0.00001 to 1.0 moles, preferably 0.0001 to 0.05 moles,preferably 0.0005 to 0.01 moles of catalyst are charged to the reactorper mole of vinyl terminated polyolefin charged.

The process is typically a solution process, although it may be a bulkor high pressure process. Homogeneous processes are preferred. (Ahomogeneous process is defined to be a process where at least 90 wt % ofthe product is soluble in the reaction media.) A bulk homogeneousprocess is particularly preferred. (A bulk process is defined to be aprocess where reactant concentration in all feeds to the reactor is 70volume % or more.) Alternately no solvent or diluent is present or addedin the reaction medium, (except for the small amounts used as thecarrier for the catalyst or other additives, or amounts typically foundwith the reactants; e.g., propane in propylene).

Suitable diluents/solvents for the process include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds such as benzene, toluene,mesitylene, and xylene. In a preferred embodiment, aliphatic hydrocarbonsolvents are preferred, such as isobutane, butane, pentane, isopentane,hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof;cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof. In anotherembodiment, the solvent is not aromatic, preferably aromatics arepresent in the solvent at less than 1 wt %, preferably at 0.5 wt %,preferably at 0 wt % based upon the weight of the solvents.

In another embodiment, the process is a slurry process. As used hereinthe term “slurry polymerization process” means a polymerization processwhere a supported catalyst is employed and monomers are polymerized onthe supported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

In a preferred embodiment, the feed concentration for the process is 60volume % solvent or less, preferably 40 volume % or less, preferably 20volume % or less.

The process may be batch, semi-batch or continuous. As used herein, theterm continuous means a system that operates without interruption orcessation. For example, a continuous process to produce a polymer wouldbe one where the reactants are continually introduced into one or morereactors and polymer product is continually withdrawn.

Useful reaction vessels include reactors (including continuous stirredtank reactors, batch reactors, reactive extruder, pipe or pump).

In a preferred embodiment, the productivity of the process is at least200 g of multiblock polyolefin of formula (X) per mmol of catalyst perhour, preferably at least 5000 g/mmol/hour, preferably at least 10,000g/mmol/hr, preferably at least 300,000 g/mmol/hr.

This invention further relates to a process, preferably an in-lineprocess, preferably a continuous process, to produce multiblockpolyolefin of formula (X), comprising introducing monomer and catalystsystem into a reactor, obtaining a reactor effluent containing vinylterminated polyolefins (preferably two or more vinyl terminatedpolyolefins), optionally removing (such as flashing off) solvent, unusedmonomer and/or other volatiles, obtaining at least two vinyl terminatedpolyolefins (such as those described herein), introducing at least twovinyl terminated polyolefins and an alkene metathesis catalyst into areaction zone (such as a reactor, an extruder, a pipe and/or a pump) andobtaining multiblock polyolefins of formula (X) (such as those describedherein).

A “reaction zone” also referred to as a “polymerization zone” is definedas an area where activated catalysts and monomers are contacted and apolymerization reaction takes place. When multiple reactors are used ineither series or parallel configuration, each reactor is considered as aseparate polymerization zone. For a multi-stage polymerization in both abatch reactor and a continuous reactor, each polymerization stage isconsidered as a separate polymerization zone. Room temperature is 23° C.unless otherwise noted.

Alkene Metathesis Catalysts

An alkene metathesis catalyst is a compound that catalyzes the reactionbetween a first vinyl terminated polyolefin with a second vinylterminated polyolefin to produce a multiblock polyolefin of formula (X),typically with the elimination of ethylene.

In a preferred embodiment, the alkene metathesis catalyst is representedby the Formula (I):

where:M is a Group 8 metal, preferably Ru or Os, preferably Ru;X and X¹ are, independently, any anionic ligand, preferably a halogen(preferably chlorine), an alkoxide or a triflate, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L and L¹ are, independently, a neutral two electron donor, preferably aphosphine or a N-heterocyclic carbene, L and L¹ may be joined to form asingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms;L and X may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;L¹ and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;R and R¹ are, independently, hydrogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);R¹ and L¹ or X¹ may be joined to form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

Preferred alkoxides include those where the alkyl group is a phenol,substituted phenol (where the phenol may be substituted with up to 1, 2,3, 4, or 5 C₁ to C₁₂ hydrocarbyl groups) or a C₁ to C₁₀ hydrocarbyl,preferably a C₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl,butyl, or phenyl.

Preferred triflates are represented by the Formula (II):

where R² is hydrogen or a C₁ to C₃₀ hydrocarbyl group, preferably a C₁to C₁₂ alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.

Preferred N-heterocyclic carbenes are represented by the Formula (III)or the Formula (IV):

where:each R⁴ is independently a hydrocarbyl group or substituted hydrocarbylgroup having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl,butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl,cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl,cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluoyl, chlorophenyl,phenol, substituted phenol, or CH₂C(CH₃)₃; andeach R⁵ is hydrogen, a halogen, or a C₁ to C₁₂ hydrocarbyl group,preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, orphenyl.

In other useful embodiments, one of the N groups bound to the carbene informula (III) or (IV) is replaced with an S, O, or P atom, preferably anS atom.

Other useful N-heterocyclic carbenes include the compounds described inHermann, W. A. Chem. Eur. J., 1996, 2, pp. 772 and 1627; Enders, D. etal. Angew. Chem. Int. Ed., 1995, 34, pg. 1021; Alder R. W., Angew. Chem.Int. Ed., 1996, 35, pg. 1121; and Bertrand, G. et al., Chem. Rev., 2000,100, pg. 39.

In a preferred embodiment, the alkene metathesis catalyst is one or moreoftricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylene]ruthenium(II)dichloride,bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylideneruthenium(II)dichloride,1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride, and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II)chloride. In a preferred embodiment, the catalyst is1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride and/orTricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II)dichloride.

In another embodiment, the alkene metathesis catalyst is represented byFormula (I) above, where: M is Os or Ru; R¹ is hydrogen; X and X¹ may bedifferent or the same and are any anionic ligand; L and L¹ may bedifferent or the same and are any neutral electron donor; and R may behydrogen, substituted or unsubstituted alkyl, or substituted orunsubstituted aryl. R is preferably hydrogen, C₁ to C₂₀ alkyl, or aryl.The C₁ to C₂₀ alkyl may optionally be substituted with one or more aryl,halide, hydroxy, C₁ to C₂₀ alkoxy, or C₂ to C₂₀ alkoxycarbonyl groups.The aryl may optionally be substituted with one or more C₁ to C₂₀ alkyl,aryl, hydroxyl, C₁ to C₅ alkoxy, amino, nitro, or halide groups. L andL¹ are preferably phosphines of the formula PR³′ R⁴′ R⁵′, where R³′ is asecondary alkyl or cycloalkyl, and R⁴′ and R^(5′) are aryl, C₁ to C₁₀primary alkyl, secondary alkyl, or cycloalkyl. R⁴′ and R⁵′ may be thesame or different. L and L¹ preferably the same and are —P(cyclohexyl)₃,—P(cyclopentyl)₃, or —P(isopropyl)₃. X and X¹ are most preferably thesame and are chlorine.

In another embodiment of the present invention, the ruthenium and osmiumcarbene compounds have the Formula (V):

where M is Os or Ru, preferably Ru; X, X¹, L, and L¹ are as describedabove; and R⁹ and R¹⁰ may be different or the same and may be hydrogen,substituted or unsubstituted alkyl, or substituted or unsubstitutedaryl. The R⁹ and R¹⁰ groups may optionally include one or more of thefollowing functional groups: alcohol, thiol, ketone, aldehyde, ester,ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups.Such compounds and their synthesis are described in U.S. Pat. No.6,111,121.

In another embodiment, the alkene metathesis catalyst useful herein maybe any of the catalysts described in U.S. Pat. Nos. 6,111,121;5,312,940; 5,342,909; 7,329,758; 5,831,108; 5,969,170; 6,759,537;6,921,735; and U.S. Patent Publication No. 2005-0261451 A1, including,but not limited to,benzylidene-bis(tricyclohexylphosphine)dichlororuthenium,benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium,dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II),(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium,1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-(2-pyridinyl)propylidene]ruthenium(II),[1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II), and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)bis(3-bromopyridine)ruthenium(II).

In another embodiment, the alkene metathesis catalyst is represented bythe formula:

where:M* is a Group 8 metal, preferably Ru or Os, preferably Ru;X* and X¹* are, independently, any anionic ligand, preferably a halogen(preferably C₁), an alkoxide or an alkyl sulfonate, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L* is N, O, P, or S, preferably N or O;R* is hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl,preferably methyl;R¹*, R²*, R³*, R⁴*, R⁵*, R⁶*, R⁷*, and R⁸* are, independently, hydrogenor a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferablymethyl, ethyl, propyl or butyl, preferably R¹*, R²*, R³*, and R⁴* aremethyl;each R⁹* and R¹³* are, independently, hydrogen or a C₁ to C₃₀hydrocarbyl or substituted hydrocarbyl, preferably a C₂ to C₆hydrocarbyl, preferably ethyl;R¹⁰*, R¹¹*, R¹²* are, independently hydrogen or a C₁ to C₃₀ hydrocarbylor substituted hydrocarbyl, preferably hydrogen or methyl;each G, is, independently, hydrogen, halogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);where any two adjacent R groups may form a single ring of up to 8non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms.

Preferably, any two adjacent R groups may form a fused ring having from5 to 8 non hydrogen atoms. Preferably the non-hydrogen atoms are Cand/or O. Preferably the adjacent R groups form fused rings of 5 to 6ring atoms, preferably 5 to 6 carbon atoms. By adjacent is meant any twoR groups located next to each other, for example R³* and R⁴* can form aring and/or R¹¹* and R¹²* can form a ring.

In a preferred embodiment, the metathesis catalyst compound comprisesone or more of:2-(2,6-diethylphenyl)-3,5,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(mesityl)-3,3,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2-isopropyl)-3,3,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2,6-diethyl-4-fluorophenyl)-3,3,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride, or mixtures thereof.

For further information on such alkene metathesis catalysts, please seeU.S. Ser. No. 12/939,054, filed Nov. 3, 2010, claiming priority to andthe benefit of U.S. Ser. No. 61/259,514, filed Nov. 9, 2009

The above named catalysts are generally available for Sigma-AldrichCorp. (St. Louis, Mo.) or Strem Chemicals, Inc. (Newburyport, Mass.).

Vinyl Terminated Polyolefins

This invention can be practiced with any vinyl containing materials,preferably with vinyl terminated polyolefins, such as vinyl terminatedethylene homo- and co-polymers, and vinyl terminated propylene homo- andco-polymers. Vinyl terminated polyolefins include homo- and co-polymersof heteroatom containing monomers, as well as polymers of olefinmonomers only. For purpose of this invention and the claims thereto, theterm vinyl terminated polyolefins (also referred to as vinyl terminatedpolymers or vinyl terminated macromers or “VTM's”) includes vinylterminated polymers and oligomers and vinyl terminated copolymers andco-oligomers. Preferred vinyl terminated polyolefins include vinylterminated isotactic polypropylene (preferably having a melting point of100° C. or more, preferably 150° C. or more), vinyl terminatedpolyethylene (preferably having a melting point of 100° C. or more,preferably 115° C. or more).

In a preferred embodiment, any vinyl terminated polyolefin describedherein has at least 75% allyl chain ends (relative to totalunsaturations), preferably at least 80%, preferably at least 85%,preferably at least 90%, preferably at least 95%.

In a preferred embodiment, any vinyl terminated polyolefin describedherein has an Mn of 200 g/mol or more, alternately from 200 to 60,000g/mol, preferably from 200 to 50,000 g/mol, preferably from 200 to40,000 g/mol, preferably from 500 to 30,000 g/mol, preferably from 1000to 10,000 g/mol.

In a preferred embodiment, the vinyl terminated polyolefin used hereincomprises at least 10 mol % (alternately at least 20 mol %, alternatelyat least 40 mol %, alternately at least 60 mol %) of a C₄ or greaterolefin (such as butene, pentene, octene, nonene, decene, undecene,dodecene, preferably C₅ to C₄₀ alpha olefin such as pentene, octene,nonene, decene, undecene, dodecene) and has: 1) at least 30% allyl chainends (relative to total unsaturations), preferably at least 40%,preferably at least 50%, preferably at least 60%, preferably at least70%, preferably at least 75%, preferably at least 80%, preferably atleast 85%, preferably at least 90%, preferably at least 95%; and 2) anMn of from 200 to 60,000 g/mol, preferably from 200 to 50,000 g/mol,preferably from 500 to 40,000 g/mol.

In a preferred embodiment, the vinyl terminated polyolefin is ahomopolymer or copolymer comprising one or more C₂ to C₄₀ olefins,preferably C₂ to C₄₀ alpha olefins, preferably ethylene, propylene,butene, pentene, hexene, octene, 1-nonene, 1-decene, 1-undecene,1-dodecene, and/or 4-methylpentene-1. In a preferred embodiment, thevinyl terminated polyolefin used herein has an Mn of from 200 to 60,000g/mol, preferably from 500 to 30,000 g/mol, preferably from 1,000 to20,000 g/mol and is a homopolymer or copolymer comprising two or more C₂to C₄₀ olefins, preferably two or more or C₃ to C₂₀ alpha olefins,preferably two or more of ethylene, propylene, butene, pentene, hexene,octene, nonene, decene, undecene, and/or dodecene and has at least 30%allyl chain ends (relative to total unsaturations), preferably at least40%, preferably at least 50%, preferably at least 60%, preferably atleast 70%, preferably at least 75%, preferably at least 80%, preferablyat least 85%, preferably at least 90%, preferably at least 95%.

In a preferred embodiment, the vinyl terminated polyolefin is a polymerhaving an Mn of from 200 to 21,000 g/mol (preferably 500 to 15,000,preferably 800 to 20,000 g/mol) comprising one or more alpha olefinsselected from the group consisting of C₂ to C₄₀ alpha olefins,preferably ethylene, propylene, butene, pentene, hexene, octene, nonene,decene, undecene, and dodecene. In a preferred embodiment, the vinylterminated polyolefin is a polymer having an Mn of from 500 to 21,000g/mol (preferably 700 to 21,000, preferably 800 to 20,000 g/mol)comprising two or more alpha olefins selected from the group consistingof C₂ to C₄₀ alpha olefins, preferably C₃ to C₂₀ alpha olefins,preferably two or more alpha olefins selected from the group consistingethylene, propylene, butene, pentene, hexene, octene, nonene, decene,undecene, and dodecene and has at least 30% allyl chain ends (relativeto total unsaturations), preferably at least 40%, preferably at least50%, preferably at least 60%, preferably at least 70%, preferably atleast 75%, preferably at least 80%, preferably at least 85%, preferablyat least 90%, preferably at least 95%.

Preferably, the vinyl terminated polyolefin is an ethylene polymer,e.g., a homo-polymer of ethylene or copolymer of ethylene and up to 50mol % (preferably from 0.5 to 25 mol %, preferably from 1 to 20 mol %)of one or more C₃ to C₄₀ alpha olefin comonomers, preferably selectedfrom the group consisting of propylene, butene, pentene, hexene, octene,nonene, decene, undecene, and dodecene. Alternately, the vinylterminated polyolefin is a propylene polymer, e.g., a homopolymer ofpropylene or copolymer of propylene and up to 50 mol % (preferably from0.5 to 25 mol %, preferably from 1 to 20 mol %) of one or more C₂ and C₄to C₄₀ alpha olefin comonomers, preferably selected from the groupconsisting of ethylene, butene, pentene, hexene, octene, nonene, decene,undecene, and dodecene. Alternately, the vinyl terminated polyolefin isa copolymer of ethylene and/or propylene and a C₄ to C₄₀ alpha-olefin,such as butene, pentene, hexene, octene, nonene, decene, undecene, anddodecene and has at least 30% allyl chain ends (relative to totalunsaturations), preferably at least 40%, preferably at least 50%,preferably at least 60%, preferably at least 70%, preferably at least75%, preferably at least 80%, preferably at least 85%, preferably atleast 90%, preferably at least 95%. Alternately, the vinyl terminatedpolyolefin is a copolymer of ethylene and/or propylene and two or moreC₄ to C₄₀ alpha olefins, such as butene, pentene, hexene, octene,nonene, decene, undecene, and dodecene. In a particularly preferredembodiment, the vinyl terminated polyolefin has at least 30% allyl chainends, relative to total unsaturations (preferably at least 40%,preferably at least 50%, preferably at least 60%, preferably at least70%, preferably at least 75%, preferably at least 80%, preferably atleast 85%, preferably at least 90%, preferably at least 95%) and thevinyl terminated polyolefin is a copolymer of:

1) ethylene and two or more C₄ to C₄₀ alpha olefins, such as butene,pentene, hexene, octene, nonene, decene, undecene, dodecene; or2) propylene and two or more C₄ to C₄₀ alpha olefins, such as butene,pentene, hexene, octene, nonene, decene, undecene, dodecene; or3) ethylene and propylene and two or more C₄ to C₄₀ alpha olefins, suchas butene, pentene, hexene, octene, nonene, decene, undecene, dodecene;or4) propylene and two or more alpha olefins selected from butene,pentene, hexene, octene, nonene, decene, undecene, and dodecene.

In a preferred embodiment, the vinyl terminated polyolefin is a polymerhaving an Mn of greater than 1,000 g/mol (preferably from 2,000 to60,000, preferably 5,000 to 50,000 g/mol) comprising one or more alphaolefins selected from the group consisting of C₂ to C₄₀ alpha olefins,preferably ethylene, propylene, butene, pentene, hexene, octene, nonene,decene, undecene, dodecene, and 4-methyl-pentene-1. Preferably, thevinyl terminated polyolefin is an ethylene polymer, e.g., a homopolymerof ethylene or copolymer of ethylene and up to 50 mol % (preferably from0.5 to 25 mol %, preferably from 1 to 20 mol %) of one or more C₃ to C₄₀alpha olefin comonomers, preferably selected from the group consistingof propylene, butene, pentene, hexene, octene, nonene, decene, undecene,dodecene, and 4-methyl-pentene-1. Alternately, the vinyl terminatedpolyolefin is propylene polymer, e.g., a homopolymer of propylene or acopolymer of propylene and up to 50 mol % (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol %) of one or more C₂ to C₄₀ alpha olefinscomonomers, preferably selected from the group consisting of ethylene,butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, and4-methyl-pentene-1 having at least 30% allyl chain ends, relative tototal unsaturations (preferably at least 40%, preferably at least 50%,preferably at least 60%, preferably at least 70%, preferably at least75%, preferably at least 80%, preferably at least 85%, preferably atleast 90%, preferably at least 95%).

In another embodiment, the vinyl terminated polyolefin useful herein maybe one or more vinyl terminated polyolefins having an Mn (measured by ¹HNMR) of 200 g/mol or more, (preferably 300 to 60,000 g/mol, 400 to50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000g/mol); and comprising: (i) from about 20 to about 99.9 mol %(preferably from about 25 to about 90 mol %, from about 30 to about 85mol %, from about 35 to about 80 mol %, from about 40 to about 75 mol %,or from about 50 to about 95 mol %) of at least one C₅ to C₄₀ olefin(preferably C₅ to C₃₀ α-olefins, more preferably C₅ to C₂₀ α-olefins,preferably, C₅ to C₁₂ α-olefins, preferably pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, preferablynorbornene, norbornadiene, and dicyclopentadiene); and (ii) from about0.1 to about 80 mol % of propylene (preferably from about 5 to about 70mol %, from about 10 to about 65 mol %, from about 15 to about 55 mol %,from about 25 to about 50 mol %, or from about 30 to about 80 mol %);wherein the vinyl terminated polyolefins has at least 40% allyl chainends, relative to total unsaturations (preferably at least 50%, at least60%, at least 70%; at least 80%, at least 90%; at least 95%); and,optionally, an isobutyl chain end to allylic chain end ratio of lessthan 0.70:1 (preferably less than 0.65:1, less than 0.60:1, less than0.50:1, or less than 0.25:1); and, further, optionally, an allyl chainend to vinylidene chain end (as determined by ¹H NMR) ratio of more than2:1 (preferably more than 2.5:1, more than 3:1, more than 5:1, or morethan 10:1); and, further, optionally, an allyl chain end to vinylenechain end ratio of greater than 10:1 (preferably greater than 15:1, orgreater than 20:1); and, even further, optionally, preferablysubstantially no isobutyl chain ends (preferably less than 0.1 wt %isobutyl chain ends). For further information on such vinyl terminatedpolyolefins please see concurrently filed U.S. Ser. No. ______ (AttorneyDocket Number 2011EM020) entitled “Vinyl Terminated Higher OlefinCopolymers and Methods to Produce Thereof.”

In another embodiment, the vinyl terminated polyolefins useful hereinmay be one or more vinyl terminated polyolefins having an Mn (measuredby ¹H NMR) of 200 g/mol or more (preferably 300 to 60,000 g/mol, 400 to50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000g/mol) and comprises: (i) from about 80 to about 99.9 mol % (preferablyabout 85 to about 99.9 mol %, more preferably about 90 to about 99.9 mol%) of at least one C₄ olefin (preferably 1-butene); and (ii) from about0.1 to 20 mol % of propylene, preferably 0.1 to 15 mol %, morepreferably 0.1 to 10 mol %; wherein the VTM has at least 40% allyl chainends relative to total unsaturations, preferably at least 50%, at least60%, at least 70%; or at least 80%; and, optionally, an isobutyl chainend to allylic chain end ratio of less than 0.70:1, less than 0.65:1,less than 0.60:1, less than 0.50:1, or less than 0.25:1; and, further,optionally, an allyl chain end to vinylidene chain end ratio of morethan 2:1, more than 2.5:1, more than 3:1, more than 5:1, or more than10:1; and, further, optionally, an allyl chain end to vinylene chain endratio of greater than 10:1 (preferably greater than 15:1, or greaterthan 20:1); and, even further, optionally, preferably, substantially noisobutyl chain ends (preferably less than 0.1 wt % isobutyl chain ends).For further information on such VTM's please see concurrently filed U.S.Ser. No. ______ (Attorney Docket Number 2011EM020) entitled “VinylTerminated Higher Olefin Copolymers and Methods to Produce Thereof.”

In particular embodiments herein, the invention relates to a compositioncomprising vinyl terminated polyolefins polymers having an Mn of atleast 200 g/mol, (preferably 200 to 100,000 g/mol, preferably 200 to75,000 g/mol, preferably 200 to 60,000 g/mol, preferably 300 to 60,000g/mol, or preferably 750 to 30,000 g/mol) (measured by ¹H NMR)comprising of one or more (preferably two or more, three or more, fouror more, and the like) C₄ to C₄₀ (preferably C₄ to C₃₀, C₄ to C₂₀, or C₄to C₁₂, preferably butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof) higher olefinderived units, where the vinyl terminated higher olefin polymercomprises substantially no propylene derived units (preferably less than0.1 wt. % propylene); and wherein the higher olefin polymer has at least5% (at least 10%, at least 15%, at least 20%, at least 30%, at least40%, at least 50%, at least 60%, at least 70% allyl; at least 80%, atleast 90%, or at least 95%) allyl chain ends, relative to totalunsaturations; and optionally, an allyl chain end to vinylidene chainend ratio of greater than 2:1 (preferably greater than 2.5:1, greaterthan 3:1, greater than 5:1, or greater than 10:1); and, further,optionally, an allyl chain end to vinylene chain end ratio of greaterthan 10:1 (preferably greater than 15:1, or greater than 20:1); and,even further, optionally, preferably substantially no isobutyl chainends (preferably less than 0.1 wt % isobutyl chain ends). In someembodiments, these higher olefin vinyl terminated polymers may compriseethylene derived units, preferably at least 5 mol % ethylene (preferablyat least 15 mol % ethylene, preferably at least 25 mol % ethylene,preferably at least 35 mol % ethylene, preferably at least 45 mol %ethylene, preferably at least 60 mol % ethylene, preferably at least 75mol % ethylene, or preferably at least 90 mol % ethylene). For furtherinformation on such vinyl terminated polyolefins please see concurrentlyfiled U.S. Ser. No. ______ (Attorney Docket Number 2011EM016) entitled“Vinyl Terminated Higher Olefin Polymers and Methods to ProduceThereof.”

In another embodiment, the vinyl terminated polyolefin useful herein isa branched polyolefin having an Mn of 7,500 to 60,000 g/mol (andoptionally a Tm of greater than 60° C. (preferably greater than 100°C.), and/or, optionally, a ΔHf of greater than 7 J/g (preferably greaterthan 50 J/g)) comprising one or more alpha olefins (preferably ethyleneand/or propylene and optionally a C₄ to C₁₀ alpha olefin), said branchedpolyolefin having: (i) 50 mol % or greater allyl chain ends, relative tototal unsaturated chain ends (preferably 60% or more, preferably 70% ormore, preferably 75% or more, preferably 80% or more, preferably 90% ormore, preferably 95% or more); (ii) a g′(vis) of 0.90 or less(preferably 0.85 or less, preferably 0.80 or less); (iii) optionally, anallyl chain end to internal vinylidene ratio of greater than 5:1(preferably greater than 10:1); and (iv) optionally, an allyl chain endto vinylidene chain end ratio of greater than 10:1 (preferably greaterthan 15:1).

In another embodiment, the vinyl terminated polyolefin useful herein isa branched polyolefin having an Mn of 60,000 g/mol or more (andoptionally a Tm of greater than 60° C. (preferably greater than 100°C.); and/or, optionally, a ΔHf of greater than 7 J/g (preferably greaterthan 50 J/g)) comprising one or more alpha olefins (preferably ethyleneand/or propylene and optionally a C₄ to C₁₀ alpha olefin); and having:(i) 50 mol % or greater allyl chain ends, relative to total unsaturatedchain ends (preferably 60% or more, preferably 70% or more, preferably75% or more, preferably 80% or more, preferably 90% or more, preferably95% or more); (ii) a g′(vis) of 0.90 or less (preferably 0.85 or less,preferably 0.80 or less); (iii) a bromine number which, upon completehydrogenation, decreases by at least 50% (preferably at least 75%); (iv)optionally, an allyl chain end to internal vinylidene ratio of greaterthan 5:1 (preferably greater than 10:1); and (v) optionally, an allylchain end to vinylidene chain end ratio of greater than 10:1, preferablygreater than 15:1).

In another embodiment, the vinyl terminated polyolefin useful herein isa branched polyolefin having an Mn of less than 7,500 g/mol, preferablyfrom 100 to 7,000 g/mol, preferably form 400 to 6,500 g/mol (andoptionally a Tm of greater than 60° C. (preferably greater than 100°C.), and/or, optionally, a ΔHf of greater than 7 J/g (preferably greaterthan 50 J/g)) comprising one or more alpha olefins (preferably ethyleneand/or propylene and optionally a C₄ to C₁₀ alpha olefin), and having:(i) 50 mol % or greater allyl chain ends, relative to total unsaturatedchain ends (preferably 60% or more, preferably 70% or more, preferably80% or more, preferably 90% or more, preferably 95% or more); (ii) aratio of percentage of saturated chain ends to percentage of allyl chainends of 1.2 to 2.0 (preferably a ratio of percentage of saturated chainends (preferably isobutyl chain ends) to percentage of allyl chain endsof 1.6 to 1.8, wherein the percentage of saturated chain ends isdetermined using ¹³C NMR as described in WO 2009/155471 at paragraph[0095] and [0096] except that the spectra are referenced to the chemicalshift of the solvent, tetrachloroethane-d₂, and/or a ratio ofMn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 or less, preferably0.85 or less, preferably 0.80 or less); (iii) optionally, a brominenumber which, upon complete hydrogenation, decreases by at least 50%(preferably by at least 75%); (iv) optionally, an allyl chain end tointernal vinylidene ratio of greater than 5:1 (preferably greater than10:1); and (v) optionally, an allyl chain end to vinylidene chain endratio of greater than 2:1 (preferably greater than 10:1), preferably thebranched vinyl terminated polyolefin has a ratio of Mn(GPC)/Mn(¹H NMR)of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less,preferably 0.80 or less).

C₄ to C₁₀ alpha olefin monomers useful in the branched polymersdescribed above include butene, pentene, hexene, heptene, octene,nonene, decene, cyclopentene, cycloheptene, cyclooctene, and isomersthereof.

For more information on useful branched polymers and methods to producethem, please see concurrently filed U.S. Ser. No. ______ (AttorneyDocket Number 2011EM034), entitled “Branched Vinyl Terminated Polymersand Methods for Production Thereof”.

In another embodiment, the vinyl terminated polyolefin consistessentially of propylene, functional group and optionally ethylene.

Alternately C₄ olefins (such as isobutylene, butadiene, n-butene) aresubstantially absent from the vinyl terminated polyolefin. AlternatelyC₄₋₂₀ olefins are substantially absent from the vinyl terminatedpolyolefin. Alternately isobutylene is substantially absent from thevinyl terminated polyolefin. By substantially absent is meant that themonomer is present in the polyolefin at 1 wt % or less, preferably at0.5 wt % or less, preferably at 0 wt %.

In another embodiment, the vinyl terminated polyolefin has a branchingindex, g′_(vis) (as determined by GPC), of 0.98 or less, alternately0.96 or less, alternately 0.95 or less, alternately 0.93 or less,alternately 0.90 or less, alternately 0.85 or less, alternately 0.80 orless, alternately 0.75 or less, alternately 0.70 or less, alternately0.65 or less, alternately 0.60 or less, alternately 0.55 or less,relative to a linear polymer of the same composition and microstructure.

In another embodiment, the vinyl terminated polyolefin preferably has aglass transition temperature (Tg) of less than 0° C. or less (asdetermined by differential scanning calorimetry as described below),preferably −10° C. or less, more preferably −20° C. or less, morepreferably −30° C. or less, more preferably −50° C. or less.

In another embodiment, the vinyl terminated polyolefin has a meltingpoint (DSC first melt) of from 30 to 200° C., alternately 40 to 180° C.,alternately 50 to 100° C. In another embodiment, the polymers describedherein have no detectable melting point by DSC following storage atambient temperature (23° C.) for at least 48 hours.

In another embodiment, the vinyl terminated polyolefins described hereinare a liquid at 25° C.

In another embodiment, the vinyl terminated polymers described hereinhave a viscosity at 60° C. of greater than 1000 cP, greater than 12,000cP, or greater than 100,000 cP. In other embodiments, the vinylterminated polymers have a viscosity of less than 200,000 cP, less than150,000 cP, or less than 100,000 cP. Viscosity is measured using aBrookfield Digital Viscometer.

In another embodiment, any of the vinyl terminated polyolefins describedor useful herein have 3-alkyl vinyl end groups (where the alkyl is a C₁to C₃₈ alkyl), also referred to as a “3-alkyl chain ends” or a “3-alkylvinyl termination”, represented by the formula:

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, preferably a C₁ to C₂₀ alkyl group, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,docecyl, and the like. The amount of 3-alkyl chain ends is determinedusing ¹³C NMR as set out below.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl chain ends(preferably at least 10%, at least 20%, at least 30%, at least 40%, atleast 50%, at least 60%, at least 70%, at least 80%, at least 90%; atleast 95%, relative to total unsaturation.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% of 3-alkyl+allyl chain ends,(e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably atleast 10%, at least 20%, at least 30%, at least 40%, at least 50%, atleast 60%, at least 70%, at least 80%, at least 90%; at least 95%,relative to total unsaturation.

In a particularly preferred embodiment, the vinyl terminated polyolefincomprises one or more of:

a) a propylene copolymer having an Mn of 300 to 30,000 g/mol (asmeasured by ¹H NMR) comprising 10 to 90 mol % propylene and 10 to 90 mol% of ethylene, wherein the polymer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in thecopolymer; and 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the copolymer; and 3) X=(1.83*(mol % ethyleneincorporated)-83), when 70 to 90 mol % ethylene is present in thecopolymer; and/orb) a propylene polymer, comprising more than 90 mol % propylene and lessthan 10 mol % ethylene, wherein the polymer has: at least 93% allylchain ends, an Mn of about 500 to about 20,000 g/mol (as measured by ¹HNMR), an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0, and less than 1400 ppm aluminum; and/orc) a propylene polymer, comprising at least 50 mol % propylene and from10 to 50 mol % ethylene, wherein the polymer has: at least 90% allylchain ends, Mn of about 150 to about 10,000 g/mol (as measured by ¹HNMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.3:1.0, wherein monomers having four or more carbon atoms are presentat from 0 to 3 mol %; and/ord) a propylene polymer, comprising at least 50 mol % propylene, from 0.1to 45 mol % ethylene, and from 0.1 to 5 mol % C₄ to C₁₂ olefin, whereinthe polymer has: at least 87% allyl chain ends (alternately at least90%), an Mn of about 150 to about 10,000 g/mol, (as measured by ¹H NMR),and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0; and/ore) a propylene polymer, comprising at least 50 mol % propylene, from 0.1to 45 mol % ethylene, and from 0.1 to 5 mol % diene, wherein the polymerhas: at least 90% allyl chain ends, an Mn of about 150 to about 10,000g/mol (as measured by ¹H NMR), and an isobutyl chain end to allylicvinyl group ratio of 0.7:1 to 1.35:1.0; and/orf) a homopolymer, comprising propylene, wherein the polymer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (asmeasured by ¹H NMR), an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum.

In a preferred embodiment, vinyl terminated polyolefins useful in thisinvention include propylene polymers, comprising propylene and less than0.5 wt % comonomer, preferably 0 wt % comonomer, wherein the polymerhas:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR (preferably 500 to 15,000,        preferably 700 to 10,000, preferably 800 to 8,000 g/mol,        preferably 900 to 7,000, preferably 1000 to 6,000, preferably        1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0; and    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

Vinyl terminated olefin polymers useful in this invention also includepropylene copolymers having an Mn of 300 to 30,000 g/mol as measured by¹H NMR (preferably 400 to 20,000, preferably 500 to 15,000, preferably600 to 12,000, preferably 800 to 10,000, preferably 900 to 8,000,preferably 900 to 7,000 g/mol), comprising 10 to 90 mol % propylene(preferably 15 to 85 mol %, preferably 20 to 80 mol %, preferably 30 to75 mol %, preferably 50 to 90 mol %) and 10 to 90 mol % (preferably 85to 15 mol %, preferably 20 to 80 mol %, preferably 25 to 70 mol %,preferably 10 to 50 mol %) of one or more alpha-olefin comonomers(preferably ethylene, butene, hexene, or octene, preferably ethylene),wherein the polymer has at least X % allyl chain ends (relative to totalunsaturations), where: 1) X=(−0.94 (mol % ethylene incorporated)+100{alternately 1.20 (−0.94 (mol % ethylene incorporated)+100), alternately1.50 (−0.94 (mol % ethylene incorporated)+100)}), when 10 to 60 mol %ethylene is present in the copolymer; and 2) X=45 (alternately 50,alternately 60), when greater than 60 and less than 70 mol % ethylene ispresent in the copolymer; and 3)

X=(1.83*(mol % ethylene incorporated)-83, {alternately 1.20 [1.83*(mol %ethylene incorporated)-83], alternately 1.50 [1.83*(mol % ethyleneincorporated)−83]}), when 70 to 90 mol % ethylene is present in thecopolymer. Alternately X is 80% or more, preferably 85% or more,preferably 90% or more, preferably 95% or more. In an alternateembodiment, the polymer has at least 80% isobutyl chain ends (based uponthe sum of isobutyl and n-propyl saturated chain ends), preferably atleast 85%, preferably at least 90%. Alternately, the polymer has anisobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,preferably 0.9:1 to 1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

Vinyl terminated olefin polymers useful in this invention also includepropylene polymers, comprising more than 90 mol % propylene (preferably95 to 99 mol %, preferably 98 to 99 mol %) and less than 10 mol %ethylene (preferably 1 to 4 mol %, preferably 1 to 2 mol %), wherein thepolymer has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 400 to about        30,000 g/mol, as measured by ¹H NMR (preferably 500 to 20,000,        preferably 600 to 15,000, preferably 700 to 10,000 g/mol,        preferably 800 to 9,000, preferably 900 to 8,000, preferably        1000 to 6,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.35:1.0; and    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

Vinyl terminated olefin polymers useful in this invention also includepropylene polymers, comprising: at least 50 (preferably 60 to 90,preferably 70 to 90) mol % propylene and from 10 to 50 (preferably 10 to40, preferably 10 to 30) mol % ethylene, wherein the polymer has:

-   -   i) at least 90% allyl chain ends (preferably at least 91%,        preferably at least 93%, preferably at least 95%, preferably at        least 98%);    -   ii) an Mn of about 150 to about 20,000 g/mol, as measured by ¹H        NMR (preferably 200 to 15,000, preferably 250 to 15,000,        preferably 300 to 10,000, preferably 400 to 9,500, preferably        500 to 9,000, preferably 750 to 9,000); and    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0, wherein monomers having four or more carbon atoms        are present at from 0 to 3 mol % (preferably at less than 1 mol        %, preferably less than 0.5 mol %, preferably at 0 mol %).

Vinyl terminated olefin polymers useful in this invention also includepropylene polymers, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(alternately at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, preferably butene), wherein the polymer has:

-   -   i) at least 90% allyl chain ends (preferably at least 91%,        preferably at least 93%, preferably at least 95%, preferably at        least 98%);    -   ii) a number average molecular weight (Mn) of about 150 to about        15,000 g/mol, as measured by ¹H NMR (preferably 200 to 12,000,        preferably 250 to 10,000, preferably 300 to 10,000, preferably        400 to 9500, preferably 500 to 9,000, preferably 750 to 9,000);        and    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.35:1.0.

Vinyl terminated olefin polymers useful in this invention also includepropylene polymers, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(alternately at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C₄ to C₁₂ alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the polymer has:

-   -   i) at least 90% allyl chain ends (preferably at least 91%,        preferably at least 93%, preferably at least 95%, preferably at        least 98%);    -   ii) a number average molecular weight (Mn) of about 150 to about        20,000 g/mol, as measured by ¹H NMR (preferably 200 to 15,000,        preferably 250 to 12,000, preferably 300 to 10,000, preferably        400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000);        and    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.7:1        to 1.35:1.0.

Any of the vinyl terminated polyolefins described herein preferably haveless than 1400 ppm aluminum, preferably less than 1000 ppm aluminum,preferably less than 500 ppm aluminum, preferably less than 100 ppmaluminum, preferably less than 50 ppm aluminum, preferably less than 20ppm aluminum, preferably less than 5 ppm aluminum.

In a preferred embodiment, the vinyl terminated polyolefin (preferably apropylene polymer) comprises less than 3 wt % of functional groupsselected from hydroxide, aryls and substituted aryls, halogens, alkoxys,carboxylates, esters, acrylates, oxygen, and carboxyl, preferably lessthan 2 wt %, more preferably less than 1 wt %, more preferably less than0.5 wt %, more preferably less than 0.1 wt %, more preferably 0 wt %,based upon the weight of the vinyl terminated polyolefin.

Preferably, the vinyl terminated polyolefin is a polymer having an M_(n)as determined by ¹H NMR of 150 to 25,000 g/mol, 200 to 20,000 g/mol,preferably 250 to 15,000 g/mol, preferably 300 to 15,000 g/mol,preferably 400 to 12,000 g/mol, preferably 750 to 10,000 g/mol. Further,a desirable molecular weight range can be any combination of any uppermolecular weight limit with any lower molecular weight limit describedabove.

In some embodiments, the vinyl terminated polyolefin contains less than80 wt % of C₄ olefin(s), (such as isobutylene n-butene, 2-butene,isobutylene, and butadiene), based upon the weight of the vinylterminated polyolefin, preferably less than 10 wt %, preferably 5 wt %,preferably less than 4 wt %, preferably less than 3 wt %, preferablyless than 2 wt %, preferably less than 1 wt %, preferably less than 0.5wt %, preferably less than 0.25 wt % of C₄ olefin(s) based upon theweight of the vinyl terminated polyolefin.

Alternately, in some embodiments, the vinyl terminated polyolefincontains less than 20 wt % of C₄ or more olefin(s), (such as C₄ to C₃₀olefins, typically such as C₄ to C₁₂ olefins, typically such as C₄, C₆,C₈, C₁₂, olefins, etc.), based upon the weight of the vinyl terminatedpolyolefin, preferably less than 10 wt %, preferably 5 wt %, preferablyless than 4 wt %, preferably less than 3 wt %, preferably less than 2 wt%, preferably less than 1 wt %, preferably less than 0.5 wt %,preferably less than 0.25 wt % of C₄ olefin(s) based upon the weight ofthe vinyl terminated polyolefin, as determined by ¹³C NMR.

In another embodiment, any vinyl terminated polyolefin compositiondescribed herein comprises less than 20 wt % dimer and trimer(preferably less than 10 wt %, preferably less than 5 wt %, morepreferably less than 2 wt %, based upon the weight of the vinylterminated polyolefin composition), as measured by Gas Chromatography.Products are analyzed by gas chromatography (Agilent 6890N withauto-injector) using helium as a carrier gas at 38 cm/sec. A columnhaving a length of 60 m (J & W Scientific DB-1, 60 m×0.25 mm I.D.×1.0 mfilm thickness) packed with a flame ionization detector (FID), anInjector temperature of 250° C., and a Detector temperature of 250° C.are used. The sample was injected into the column in an oven at 70° C.,then heated to 275° C. over 22 minutes (ramp rate 10° C./min to 100° C.,30° C./min to 275° C., hold). An internal standard, usually the monomer,is used to derive the amount of dimer or trimer product that isobtained. Yields of dimer and trimer product are calculated from thedata recorded on the spectrometer. The amount of dimer or trimer productis calculated from the area under the relevant peak on the GC trace,relative to the internal standard.

In another embodiment, any vinyl terminated polyolefin described hereincontains less than 25 ppm hafnium, preferably less than 10 ppm hafnium,preferably less than 5 ppm hafnium based on the yield of polymerproduced and the mass of catalyst employed.

In another embodiment, any vinyl terminated polyolefins described hereinmay have a melting point (DSC first melt) of from 60 to 165° C.,alternately 50 to 120° C. In another embodiment, the vinyl terminatedpolyolefins described herein have no detectable melting point by DSCfollowing storage at ambient temperature (23° C.) for at least 48 hours.

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning Calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., then heated at a heating rate of 10°C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified.

Particularly useful vinyl terminated polyolefins may be isotactic,highly isotactic, syndiotactic, or highly syndiotactic propylenepolymer, particularly isotactic polypropylene. As used herein,“isotactic” is defined as having at least 10% isotactic pentads,preferably having at least 40% isotactic pentads of methyl groupsderived from propylene according to analysis by ¹³C NMR. As used herein,“highly isotactic” is defined as having at least 60% isotactic pentadsaccording to analysis by ¹³C NMR. In a desirable embodiment, themultiblock polyolefin has at least 85% isotacticity. As used herein,“syndiotactic” is defined as having at least 10% syndiotactic pentads,preferably at least 40%, according to analysis by ¹³C NMR. As usedherein, “highly syndiotactic” is defined as having at least 60%syndiotactic pentads according to analysis by ¹³C NMR. In anotherembodiment, the multiblock polyolefin has at least 85% syndiotacticity.

In another embodiment, the polymers described herein have an Mw(measured as described below) of 1,000 to about 60,000 g/mol,alternately 2000 to 25,000 g/mol, alternately 3,000 to 20,000 g/moland/or an Mz of about 1700 to about 150,000 g/mol, alternately 800 to100,000 g/mol.

Mw, Mn, Mz, number of carbon atoms, and g′_(vis) are determined by GelPermeation Chromatography (GPC) using a High Temperature Size ExclusionChromatograph (either from Waters Corporation or Polymer Laboratories),equipped with three in-line detectors, a differential refractive indexdetector (DRI), a light scattering (LS) detector, and a viscometer.Experimental details, including detector calibration, are described in:T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules,Volume 34, Number 19, pp. 6812-6820, (2001) and references therein.Three Polymer Laboratories PLgel 10 mm Mixed-B LS columns are used. Thenominal flow rate is 0.5 cm³/min and the nominal injection volume is 300μL. The various transfer lines, columns and differential refractometer(the DRI detector) are contained in an oven maintained at 145° C.Solvent for the experiment is prepared by dissolving 6 grams ofbutylated hydroxy toluene as an antioxidant in 4 liters of Aldrichreagent grade 1, 2, 4 trichlorobenzene (TCB). The TCB mixture is thenfiltered through a 0.7 μm glass pre-filter and subsequently through a0.1 μm Teflon filter. The TCB is then degassed with an online degasserbefore entering the Size Exclusion Chromatograph. Polymer solutions areprepared by placing dry polymer in a glass container, adding the desiredamount of TCB, then heating the mixture at 160° C. with continuousagitation for about 2 hours. All quantities are measuredgravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/ml at room temperatureand 1.324 g/ml at 145° C. The injection concentration is from 0.75 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples. Prior to running each sample the DRI detector and theinjector are purged. Flow rate in the apparatus is then increased to 0.5ml/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The LS laser is turned on 1 to 1.5 hoursbefore running the samples. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,I_(DRI), using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers,0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mol, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(θ) is the form factor for amonodisperse random coil, and K_(O) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{{dn}/d}\; c} \right)}^{2}}{\lambda^{4}N_{A}}$

where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits. The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(V) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forfurther guidance on selecting a linear standard having similar molecularweight and comonomer content and determining k coefficients and aexponents.

For more information on useful vinyl terminated polyolefins usefulherein please see U.S. Ser. No. 12/143,663, filed Jun. 20, 2008, andconcurrently filed U.S. Ser. No. ______ Attorney Docket Number2011EM016, entitled “Vinyl Terminated Higher Olefin Polymers and Methodsto Produce Thereof”, and concurrently filed U.S. Ser. No. ______Attorney Docket Number 2011EM020, entitled “Vinyl Terminated HigherOlefin Copolymers and Methods to Produce Thereof”, and concurrentlyfiled U.S. Ser. No. ______ Attorney Docket Number 2011EM034 entitled“Branched Vinyl Terminated Polymers and Methods for Production Thereof”.

Process to Make Vinyl Terminated Polyolefins

The vinyl terminated polyolefins described above are typically preparedin a homogeneous process, preferably a bulk process, as described inU.S. Ser. No. 12/143,663, filed on Jun. 20, 2008, which is incorporatedby reference herein. Vinyl terminated polyolefins may also be producedusing the processes (and catalyst compounds and/or activators) disclosedin concurrently filed U.S. Ser. No. ______, Attorney docket number(2011EM011) entitled “Novel Catalysts and Methods of use Thereof toProduce Vinyl Terminated Polymers” and U.S. Ser. No. ______, Attorneydocket number 2011EM013, entitled “Enhanced Catalyst Performance forProduction of Vinyl Terminated Propylene and Ethylene/PropyleneMacromers”. Useful vinyl terminated polyolefins can also be producedusing the processes disclosed in concurrently filed U.S. Ser. No. ______Attorney Docket Number 2011EM016, entitled “Vinyl Terminated HigherOlefin Polymers and Methods to Produce Thereof”, and concurrently filedU.S. Ser. No. ______ Attorney Docket Number 2011EM020, entitled “VinylTerminated Higher Olefin Copolymers and Methods to Produce Thereof”, andconcurrently filed U.S. Ser. No. ______ Attorney Docket Number 2011EM034entitled “Branched Vinyl Terminated Polymers and Methods for ProductionThereof”.

In a preferred embodiment, one, two or three or more C₂ to C₄₀ alphaolefins, such as ethylene, propylene, butene, pentene, hexene, octene,decene and dodecene (preferably ethylene and/or propylene and optionalcomonomers (such as one, two or three or more of ethylene, butene,hexene, octene, decene and dodecene)) can be polymerized/polymerized byreacting a catalyst system (comprising metallocene compound(s), and oneor more activators) with the olefins. Other additives may also be used,as desired, such as scavengers and/or hydrogen. Any conventionalsuspension, homogeneous bulk, solution, slurry, or high-pressurepolymerization process can be used. Such processes can be run in abatch, semi-batch, or continuous mode. Such processes and modes are wellknown in the art. Homogeneous polymerization processes are preferred. Abulk homogeneous process is particularly preferred. Alternately, nosolvent or diluent is present or added in the reaction medium, (exceptfor the small amounts used as the carrier for the catalyst system orother additives, or amounts typically found with the monomer; e.g.,propane in propylene).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopars); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, and 1-decene. Mixtures of the foregoing are also suitable. Ina preferred embodiment, aliphatic hydrocarbon solvents are preferred,such as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably less than 0.5 wt %, preferably at 0 wt %based upon the weight of the solvents.

In another embodiment, the process is a slurry process. As used hereinthe term “slurry polymerization process” means a polymerization processwhere a supported catalyst is employed and monomers are polymerized onthe supported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

In a preferred embodiment, the feed concentration for the polymerizationis 60 volume % solvent or less, preferably 40 volume % or less,preferably 20 volume % or less. Preferably the polymerization is run ina bulk process.

Suitable additives to the polymerization process can include one or morescavengers, promoters, modifiers, reducing agents, oxidizing agents,hydrogen, aluminum alkyls, or silanes.

In a preferred embodiment, little or no scavenger is used in the processto produce the vinyl terminated polyolefin. Preferably, scavenger ispresent at zero mol %, alternately the scavenger is present at a molarratio of scavenger metal to transition metal of less than 100:1,preferably less than 50:1, preferably less than 15:1, preferably lessthan 10:1.

In a preferred embodiment, little or no alumoxane is used in the processto produce the vinyl terminated polymers. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1.

In an alternate embodiment, if an alumoxane is used to produce the vinylterminated polymers then, the alumoxane has been treated to remove freealkyl aluminum compounds, particularly trimethyl aluminum.

In a preferred embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172.4 kPa), more preferably 0.1to 10 psig (0.7 to 68.95 kPa). It has been found that in the presentsystems, hydrogen can be used to provide increased activity withoutsignificantly impairing the catalyst's ability to produce allylic chainends. Preferably the catalyst activity (calculated as g/mmolcatalyst/hr)is at least 20% higher than the same reaction without hydrogen present,preferably at least 50% higher, preferably at least 100% higher.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

In an alternate embodiment, the activity of the catalyst is at least 50g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr. In an alternateembodiment, the conversion of olefin monomer is at least 10%, based uponpolymer yield and the weight of the monomer entering the reaction zone,preferably 20% or more, preferably 30% or more, preferably 50% or more,preferably 80% or more.

In an alternate embodiment, the productivity at least 4500 g/mmol/hour,preferably 5000 or more g/mmol/hour, preferably 10,000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr. In an alternateembodiment, the productivity is at least 80,000 g/mmol/hr, preferably atleast 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr,preferably at least 250,000 g/mmol/hr, preferably at least 300,000g/mmol/hr.

In a preferred embodiment, the productivity of the process is at least200 g of vinyl terminated polyolefin per mmol of catalyst per hour,preferably at least 5000 g/mmol/hour, preferably at least 10,000g/mmol/hr, preferably at least 300,000 g/mmol/hr.

Preferred polymerizations can be run at typical temperatures and/orpressures, such as from 25 to 150° C., preferably 40 to 120° C.,preferably 45 to 80° C., and preferably from 0.35 to 10 MPa, preferablyfrom 0.45 to 6 MPa, preferably from 0.5 to 4 MPa.

In a typical polymerization, the residence time of the reaction is up to60 minutes, preferably between 5 to 50 minutes, preferably 10 to 40minutes.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (preferably 25 to 150° C., preferably 40 to120° C., preferably 45 to 80° C.); and 2) is conducted at a pressure ofatmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferablyfrom 0.45 to 6 MPa, preferably from 0.5 to 4 MPa); and 3) is conductedin an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; preferably where aromatics are present in the solvent at lessthan 1 wt %, preferably less than 0.5 wt %, preferably less than 0 wt %based upon the weight of the solvents); and 4) wherein the catalystsystem used in the polymerization comprises less than 0.5 mol %,preferably 0 mol % alumoxane, alternately the alumoxane is present at amolar ratio of aluminum to transition metal less than 500:1, preferablyless than 300:1, preferably less than 100:1, preferably less than 1:1);and 5) the polymerization occurs in one reaction zone; and 6) theproductivity of the catalyst compound is at least 80,000 g/mmol/hr(preferably at least 150,000 g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least300,000 g/mmol/hr); and 7) optionally scavengers (such as trialkylaluminum compounds) are absent (e.g., present at zero mol %, alternatelythe scavenger is present at a molar ratio of scavenger metal totransition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1); and 8) optionallyhydrogen is present in the polymerization reactor at a partial pressureof 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig(0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)). Inpreferred embodiment, the catalyst system used in the polymerizationcomprises no more than one catalyst compound. A “reaction zone” alsoreferred to as a “polymerization zone” is a vessel where polymerizationtakes place, for example a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Ina preferred embodiment, the polymerization occurs in one reaction zone.Room temperature is 23° C. unless otherwise noted.

Catalyst Compounds to Make Vinyl Terminated Polyolefins

Catalyst compounds useful herein to produce the vinyl terminatedpolyolefins include one or more metallocene compound(s) represented bythe formulae:

where:Hf is hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines,ethers, or a combination thereof, preferably methyl, ethyl, propyl,butyl, phenyl, benzyl, chloride, bromide, iodide, (alternately two X'smay form a part of a fused ring or a ring system);each Q is, independently carbon or a heteroatom, preferably C, N, P, S(preferably at least one Q is a heteroatom, alternately at least two Q'sare the same or different heteroatoms, alternately at least three Q'sare the same or different heteroatoms, alternately at least four Q's arethe same or different heteroatoms);each R¹ is, independently, hydrogen or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, R¹ may the same ordifferent as R²;each R² is, independently, hydrogen or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided that at leastone of R¹ or R² is not hydrogen, preferably both of R¹ and R² are nothydrogen, preferably R¹ and/or R² are not branched;each R³ is, independently, hydrogen, or a substituted or unsubstitutedhydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, provided, however, that at least three R³ groups are nothydrogen (alternately four R³ groups are not hydrogen, alternately fiveR³ groups are not hydrogen);{Alternately, when the catalyst compound is to used to make thehomo-polymer then each R³ is, independently, hydrogen, or a substitutedor unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,preferably 1 to 6 carbon atoms, preferably a substituted orunsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, provided, however, that: 1)all five R³ groups are methyl; or 2) four R³ groups are not hydrogen andat least one R³ group is a C₂ to C₈ substituted or unsubstitutedhydrocarbyl (preferably at least two, three, four or five R³ groups area C₂ to C₈ substituted or unsubstituted hydrocarbyl)};each R⁴ is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group,preferably a substituted or unsubstituted hydrocarbyl group having from1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably asubstituted or unsubstituted C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substitutedphenyl (such as propyl phenyl), phenyl, silyl, substituted silyl, (suchas CH₂SiR′, where R′ is a C₁ to C₁₂ hydrocarbyl, such as methyl, ethyl,propyl, butyl, phenyl);R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl or octyl;each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided however that atleast seven R⁷ groups are not hydrogen, alternately at least eight R⁷groups are not hydrogen, alternately all R⁷ groups are not hydrogen,(preferably the R⁷ groups at the 3 and 4 positions on each Cp ring ofFormula IV are not hydrogen);N is nitrogen;R₂ ^(a)T is a bridge, preferably T is Si or Ge, preferably Si, and eachR^(a), is independently, hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,phenyl, benzyl, substituted phenyl, and two R^(a) can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system; and further provided that any two adjacent Rgroups may form a fused ring or multicenter fused ring system where therings may be aromatic, partially saturated or saturated.

In an alternate embodiment, at least one R⁴ group is not hydrogen,alternately at least two R⁴ groups are not hydrogen, alternately atleast three R⁴ groups are not hydrogen, alternately at least four R⁴groups are not hydrogen, alternately all R⁴ groups are not hydrogen.

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

-   (1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-Dimethylindenyl)(tetramethylcyclopentadienyl)hafniumdimethyl,-   (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-Dimethylindenyl)(tetramethylpropylcyclopentadienyl)hafniumdimethyl,-   (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (9-Methylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   μ-Dihydrosilyl-bis(tetramethylcyclopentadienyl)hafniumdimethyl,-   μ-Dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)    hafniumdimethyl, and-   μ-Dicyclopropylsilyl(bis    tetramethylcyclopentadienyl)hafniumdimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride, dibromide, or difluoride) or a bisphenoxide, particularlyfor use with an alumoxane activator.

Preferred activators useful with the above include:dimethylaniliniumtetrakis(pentafluorophenyl)borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B](where Ph is phenyl and Me is methyl).

In another embodiment, the vinyl terminated polyolefins useful here inmay be produced using the catalyst compound represented by the formula:

where M is hafnium or zirconium (preferably hafnium); each X is,independently, selected from the group consisting of hydrocarbylradicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides,sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and acombination thereof, (two X's may form a part of a fused ring or a ringsystem) (preferably each X is independently selected from halides and C₁to C₅ alkyl groups, preferably each X is a methyl group); each R⁸ is,independently, a C₁ to C₁₀ alkyl group (preferably methyl, ethyl,propyl, butyl, pentyl, hexyl, or isomers thereof, preferably each R⁸ isa methyl group); each R⁹ is, independently, a C₁ to C₁₀ alkyl group(preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomersthereof, preferably each R⁹ is a n-propyl group); each R¹⁰ is hydrogen;each R¹¹, R¹², and R¹³, is, independently, hydrogen or a substituted orunsubstituted hydrocarbyl group, a heteroatom or heteroatom containinggroup (preferably hydrogen); T is a bridging group (preferably T isdialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon);and further provided that any of adjacent R¹¹, R¹², and R¹³ groups mayform a fused ring or multicenter fused ring system where the rings maybe aromatic, partially saturated or saturated. For further informationon such catalyst compounds and their use to make vinyl terminatedmacromers, please see concurrently filed U.S. Ser. No. ______ (AttorneyDocket Number 2011EM011), entitled “Novel Catalysts and Methods of UseThereof to Produce Vinyl Terminated Polymers”.

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

rac-dimethylsilyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,

-   rac-dimethylsilyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl    bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl    bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-methylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-methylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)zirconiumdimethyl,-   rac-dimethylsilylbis(2-propyl,3-butylindenyl)hafniumdimethyl,-   rac-dimethylsilylbis(2-propyl,3-butylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2,3-dimethyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2,3-dimethyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-propyl,3-methylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-propyl,3-methylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-propyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-propyl,3-ethylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-propyl,3-butylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-propyl,3-butylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-butylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2,3-dimethyl)hafniumdimethyl, and-   rac-dimethylgermanyl bis(2,3-dimethyl)zirconiumdimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide, particularly for usewith an alumoxane activator.

In particular embodiments, the catalyst compound israc-dimethylsilylbis(2-methyl,3-propylindenyl)hafniumdimethyl ordichloride, orrac-dimethylsilylbis(2-methyl,3-propylindenyl)zirconiumdimethyl ordichloride.

Preferred activators useful with the above include:dimethylaniliniumtetrakis(pentafluorophenyl)borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B](where Ph is phenyl and Me ismethyl).

Preferred combinations of catalyst and activator include:N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate andrac-dimethylsilylbis(2-methyl,3-propylindenyl)hafniumdimethyl, orrac-dimethylsilylbis(2-methyl,3-propylindenyl)zirconiumdimethyl.

In another embodiment, the vinyl terminated polyolefins useful here inmay be produced using the catalyst compound represented by the formula:

wherein M is hafnium or zirconium; each X is, independently, selectedfrom the group consisting of hydrocarbyl radicals having from 1 to 20carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halogens, dienes, amines, phosphines, ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group (preferablya C₁ to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,pentyl, hexyl, heptyl, or octyl); and each R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ are, independently, hydrogen, or asubstituted or unsubstituted hydrocarbyl group having from 1 to 8 carbonatoms (preferably 1 to 6 carbon atoms, preferably a substituted orunsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl). In a preferred embodiment,at least three of R²⁴-R²⁸ groups are not hydrogen (alternately four ofR²⁴-R²⁸ groups are not hydrogen, alternately five of R²⁴-R²⁸ groups arenot hydrogen). In a preferred embodiment, all five groups of R²⁴-R²⁸ aremethyl. In a preferred embodiment, four of the R²⁴-R²⁸ groups are nothydrogen and at least one of the R²⁴-R²⁸ groups is a C₂ to C₈substituted or unsubstituted hydrocarbyl (preferably at least two,three, four or five of R²⁴-R²⁸ groups are a C₂ to C₈ substituted orunsubstituted hydrocarbyl). In another preferred embodiment, R¹⁵ and R¹⁷are methyl groups, R¹⁶ is a hydrogen, R¹⁸-R²³ are all hydrogens, R²⁴-R²⁸are all methyl groups, and each X is a methyl group. For furtherinformation on such catalyst compounds and their use to make vinylterminated macromers, please see concurrently filed U.S. Ser. No. ______(Attorney Docket Number 2011EM013) entitled “Enhanced CatalystPerformance for Production of Vinyl Terminated Propylene andEthylene/Propylene Macromers.”

Catalyst compounds that are particularly useful in this inventioninclude (CpMes)(1,3-Me₂ benz[e]indenyl)HfMe₂,(CpMes)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMes)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂, (CpMe₅)(1-methyl,3-ethylbenz[e]indenyl)HfMe₂, (CpMe₄ n-propyl)(1,3-Me₂benz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl) (1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl) (1-ethyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl, 3-ethylbenz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1,3-Me₂ benz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂, (CpMe₄ n-butyl)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-methyl,3-ethylbenz[e]indenyl)HfMe₂, and the zirconium analogsthereof.

In an alternate embodiment, the “dimethyl” (Me₂) after the transitionmetal in the list of catalyst compounds above is replaced with adihalide (such as dichloride or difluoride) or a bisphenoxide,particularly for use with an alumoxane activator.

Other activators useful with the above catalysts include:dimethylaniliniumtetrakis(pentafluorophenyl)borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B].

In a preferred embodiment, the branched polymers described herein may beproduced as described in concurrently filed U.S. Ser. No. ______(Attorney Docket Number 2011EM034) entitled “Branched Vinyl TerminatedPolymers and Methods for Production Thereof”.

With regard to the above catalyst compounds, the term “substituted”means that a hydrogen group has been replaced with a hydrocarbyl group,a heteroatom or a heteroatom containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group andethyl alcohol is an ethyl group substituted with an —OH group.

Activators and Activation Methods for Catalyst Compounds to Make VinylTerminated Polymers

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract one reactive, c-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally polymeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. Another alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is a 1:1 molar ratio. Alternatepreferred ranges include up to 500:1, alternately up to 200:1,alternately up to 100:1 alternately from 1:1 to 50:1.

In a preferred embodiment, little or no alumoxane is used in the processto produce the vinyl terminated polyolefin. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1.

In an alternate embodiment, if an alumoxane is used to produce the VTM'sthen, the alumoxane has been treated to remove free alkyl aluminumcompounds, particularly trimethyl aluminum.

Further, in a preferred embodiment, the activator used herein to producethe vinyl terminated polyolefin is bulky as defined herein and isdiscrete.

Aluminum alkyl or organoaluminum compounds which may be utilized asco-activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, and the like. Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic non-coordinating anion (asdefined in U.S. Ser. No. 12/143,663, filed on Jun. 20, 2008), such astri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a trisperfluorophenyl boron metalloid precursor or a tris perfluoronapthylboron metalloid precursor, polyhalogenated heteroborane anions (WO98/43983), boric acid (U.S. Pat. No. 5,942,459) or combination thereof.It is also within the scope of this invention to use neutral or ionicactivators alone or in combination with alumoxane or modified alumoxaneactivators. Preferably the activator is N,N-dimethylaniliniumtetrakis(perfluoronapthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate. For additional activators usefulherein, please see U.S. Ser. No. 12/143,663, filed on Jun. 20, 2008.

In another embodiment, the activator is a bulky activator represented bythe formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(s), where V_(s) is the scaledvolume. V_(s) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(s) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

MV Molecular Per Total Structure of boron Formula of each subst. MVActivator substituents substituent V_(s) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoro- naphthyl)borate

C₁₀F₇  34 261 1044 Dimethylanilinium tetrakis(perfluoro- biphenyl)borate

C₁₂F₉  42 349 1396 [4-t-butyl- PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B],and the types disclosed in U.S. Pat. No. 7,297,653.

The typical activator-to-catalyst-precursor ratio is a 1:1 molar ratiofor non-alumoxane activators. Alternate preferred ranges include from0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to500:1 alternately from 1:1 to 1000:1. A particularly useful range isfrom 0.5:1 to 10:1, preferably 1:1 to 5:1.

Support Materials

In embodiments herein, the catalyst system to make the vinyl terminatedpolyolefin may comprise an inert support material. Preferably thesupported material is a porous support material, for example, talc, andinorganic oxides. Other support materials include zeolites, clays,organoclays, or any other organic or inorganic support material and thelike, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxidessuch as silica, alumina and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably, the surface area of the support material is in therange is from about 100 to about 400 m²/g, pore volume from about 0.8 toabout 3.0 cc/g and average particle size is from about 5 to about 100μm. The average pore size of the support material useful in theinvention is in the range of from 10 to 1000 Å, preferably 50 to about500 Å, and most preferably 75 to about 350 Å. In some embodiments, thesupport material is a high surface area, amorphous silica (surfacearea=300 m²/gm; pore volume of 1.65 cm³/gm), examples of which aremarketed under the tradenames of DAVISON 952 or DAVISON 955 by theDavison Chemical Division of W.R. Grace and Company. In otherembodiments, DAVISON 948 is used.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce the catalyst system of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

Methods of Making the Supported Catalyst Systems

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator.The slurry of the support material in the solvent is prepared byintroducing the support material into the solvent, and heating themixture to about 0 to about 70° C., preferably to about 25 to about 60°C., preferably at room temperature. Contact times typically range fromabout 0.5 hours to about 24 hours, from about 0.5 hours to about 8hours, or from about 0.5 hours to about 4 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene and ethylbenzene, may also be employed.

In embodiments herein, the support material is contacted with a solutionof a metallocene compound and an activator, such that the reactivegroups on the support material are titrated, to form a supportedpolymerization catalyst. The period of time for contact between themetallocene compound, the activator, and the support material is as longas is necessary to titrate the reactive groups on the support material.To “titrate” is meant to react with available reactive groups on thesurface of the support material, thereby reducing the surface hydroxylgroups by at least 80%, at least 90%, at least 95%, or at least 98%. Thesurface reactive group concentration may be determined based on thecalcining temperature and the type of support material used. The supportmaterial calcining temperature affects the number of surface reactivegroups on the support material available to react with the metallocenecompound and an activator: the higher the drying temperature, the lowerthe number of sites. For example, where the support material is silicawhich, prior to the use thereof in the first catalyst system synthesisstep, is dehydrated by fluidizing it with nitrogen and heating at about600° C. for about 16 hours, a surface hydroxyl group concentration ofabout 0.7 millimoles per gram (mmols/gm) is typically achieved. Thus,the exact molar ratio of the activator to the surface reactive groups onthe carrier will vary. Preferably, this is determined on a case-by-casebasis to assure that only so much of the activator is added to thesolution as will be deposited onto the support material without leavingexcess of the activator in the solution.

The amount of the activator which will be deposited onto the supportmaterial without leaving excess in the solution can be determined in anyconventional manner, e.g., by adding the activator to the slurry of thecarrier in the solvent, while stirring the slurry, until the activatoris detected as a solution in the solvent by any technique known in theart, such as by ¹H NMR. For example, for the silica support materialheated at about 600° C., the amount of the activator added to the slurryis such that the molar ratio of B to the hydroxyl groups (OH) on thesilica is about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1,more preferably about 0.9:1 to about 2:1 and most preferably about 1:1.The amount of boron on the silica may be determined by using ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, Eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644. In another embodiment, it is alsopossible to add such an amount of activator which is in excess of thatwhich will be deposited onto the support, and then remove, e.g., byfiltration and washing, any excess of the activator.

In another embodiment, a vinyl terminated polyolefin can be produced bythe method disclosed in Macromol. Chem. Phys. 2010, 211, pp. 1472-1481.

The following paragraphs enumerated provide for various aspects of thepresent invention.

1. A composition comprising a multiblock polyolefin represented by theformula (X):

PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X),

or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen;PO and PO* are each, independently, polyolefins, preferably derived fromvinyl terminated polyolefins, preferably PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms, provided that at least one of PO and PO* are C₂₀or greater, said multiblock polyolefin having:

1) an internal unsaturation as shown by the ¹³C NMR peak at betweenabout 128 and about 132 ppm (alternately the multiblock polyolefin has0.10 to 35 internal unsaturations per 1,000 carbon atoms, preferably 0.2to 20, preferably 0.3 to 10, as determined by ¹³C NMR);

2) an Mn ratio “Z”=0.1 to 10, preferably 0.25 to 4, preferably 0.5 to 2,preferably 0.75 to 1.5, where Z is the Mn (as determined by ¹³C NMR)divided by Mn (as determined according to Gel Permeation Chromotographyusing polystyrene standards); and

3) optionally, from 0.30 (J) and 0.75 (J) (preferably from 0.35 (J) and0.70 (J), preferably from 0.40 (J) and 0.60 (J)) internal unsaturationsper 1000 carbons as determined by ¹H NMR spectroscopy, where J is thenumber of reactive groups per 1000 carbons for the mixture of vinylterminated polyolefins, that preferably become PO and PO*, before theyare coupled by an alkene metathesis catalyst.

2. The composition of paragraph 1, wherein PO* is PO.3. The composition of paragraph 1, wherein PO is different from PO*.4. The composition of paragraph 1, wherein the multiblock polyolefin isa mixture of PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*,PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO andPO*—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*.5. The composition of paragraph 4, wherein the mixture comprises about30% to about 70% of PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*, about1% to about 30% of PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO and about1% to about 30% PO*—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*.6. The composition of any of paragraphs 1 through 5, wherein each ofR¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is a hydrogen, alternately wherein atleast two of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are hydrogen atoms,alternately, wherein at least four of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶are hydrogen atoms, alternately wherein R¹³ and R¹⁴ are hydrogen atoms.7. The composition of any of paragraphs 1 through 6, wherein themultiblock polyolefin shows two crystallization temperatures (Tc)according to the DSC and the Tc's are different by at least 5° C.,preferably by at least 10° C., preferably by at least 20° C., preferablyby at least 30° C., preferably by at least 40° C., preferably by atleast 50° C., preferably by at least 60° C., preferably by at least 70°C., preferably by at least 80° C.8. The composition of any of paragraphs 1 through 7, wherein the heat offusion (Hf), determined by DSC, of the multiblock polyolefin is betweenthe Hfs of the starting vinyl terminated polyolefins (preferably, the Hfof the multiblock polyolefin is at least 5 J/g different than the Hf ofthe starting vinyl terminated polyolefin having the highest Hf,preferably at least 10 J/g different, preferably at least 20 J/gdifferent, preferably at least 50 J/g different, preferably at least 80J/g different; alternately, the Hf of the multiblock polyolefin is atleast 5 J/g less than the Hf of the starting vinyl terminated polyolefinhaving the highest Hf, preferably at least 10 J/g less, preferably atleast 20 J/g less, preferably at least 30 J/g less, preferably at least40 J/g less, preferably at least 50 J/g less, preferably at least 60 J/gless, preferably at least 70 J/g less, preferably at least 80 J/g less,preferably at least 90 J/g less.9. The composition of any of paragraphs 1 to 8, the comonomer content ofthe multiblock polyolefin is at least 5 mol % different than thecomonomer content of the starting vinyl terminated polyolefin having thehighest comonomer content, preferably at least 10 mol % different,preferably at least 20 mol % different, preferably at least 30 mol %different, preferably at least 40 mol % different.10. The composition of paragraph 4, wherein the multiblock polyolefinhas two peak melting temperatures (Tm) and the Tm's are different by atleast 5° C., preferably by at least 10° C., preferably by at least 20°C., preferably by at least 30° C., preferably by at least 40° C.,preferably by at least 50° C., preferably by at least 60° C., preferablyby at least 70° C., preferably by at least 80° C.11. The composition of any of paragraphs 1 through 10, wherein themultiblock polyolefin PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO* has aMn from 1000 to 60,000 g/mol, alternately 10,000 to 45,000 g/mol,alternately from 20,000 to 42,000 g/mol, preferably about 40,000 g/mol.12. The composition of any of paragraphs 1 through 10, wherein themultiblock polyolefin PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO* has aMn of about 20,000 g/mol.13. The composition of any of paragraphs 1 through 10, wherein themultiblock polyolefin PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO* has aMn of about 1,000 g/mol.14. The composition of any of paragraphs 1 through 10, wherein PO is apolypropylene of a Mn of about 300 to about 20,000 g/mol.15. The composition of any of paragraphs 1 through 10, wherein PO is anethylene/propylene copolymer of a Mn of about 300 to about 20,000 g/mol.16. The composition of any of paragraphs 1 through 10, wherein at leastone PO and PO* is a substituted or unsubstituted hydrocarbyl groupshaving 2 to 18 carbon atoms.17. A process to prepare a multiblock polyolefin of any of the aboveparagraphs 1 to 16, preferably represented by the formula (X):

PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X),

or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen;PO and PO* are each, independently, polyolefins, preferably derived fromvinyl terminated polyolefins, preferably PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms, provided that at least one of PO and PO* are C₂₀or greater, said multiblock polyolefin having:

1) an internal unsaturation as shown by the ¹³C NMR peak at betweenabout 128 and about 132 ppm;

2) an Mn ratio “Z”=0.1 to 10, preferably 0.25 to 4, preferably 0.5 to 2,preferably 0.75 to 1.5, where Z is the Mn (as determined by ¹³C NMR)divided by Mn (as determined according to Gel Permeation Chromotographyusing polystyrene standards); and

3) optionally, from 0.30 (J) and 0.75 (J) (preferably from 0.35 (J) and0.70 (J), preferably from 0.40 (J) and 0.60 (J)) internal unsaturationsper 1000 carbons as determined by ¹H NMR spectroscopy, where J is thenumber of reactive groups per 1000 carbons for the mixture of vinylterminated polyolefins, that preferably become PO and PO*, before theyare coupled by an alkene metathesis catalyst, comprising the step of:

contacting an alkene metathesis catalyst with two or more vinylterminated polyolefins each comprising at least 30% allyl chain ends(relative to total unsaturations) preferably at least 40%, preferably atleast 50%, preferably at least 60%, preferably at least 70%, preferablyat least 75%, preferably at least 80%, preferably at least 85%,preferably at least 90%, preferably at least 95%.

18. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 15 wt % to about 95 wt %ethylene and has more than 80% allyl chain ends (relative to totalunsaturations).19. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 30 wt % to about 95 wt %ethylene and has more than 70% allyl chain ends (relative to totalunsaturations).20. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 30 wt % to about 95 wt %ethylene and has more than 90% allyl chain ends (relative to totalunsaturations).21. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 15 wt % to about 95 wt %propylene and has more than 80% allyl chain ends (relative to totalunsaturations).22. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 30 wt % to about 95 wt %propylene and has more than 70% allyl chain ends (relative to totalunsaturations).23. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 30 wt % to about 95 wt %propylene and has more than 90% allyl chain ends (relative to totalunsaturations).24. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 15 wt % to about 95 wt %ethylene-propylene copolymer and has more than 80% allyl chain ends(relative to total unsaturations).25. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 30 wt % to about 95 wt %ethylene-propylene copolymer and has more than 70% allyl chain ends(relative to total unsaturations).26. The process of paragraph 17, wherein at least one of the two or morevinyl terminated polyolefins comprises about 30 wt % to about 95 wt %ethylene-propylene copolymer as have more than 90% allyl chain ends(relative to total unsaturations).27. The process of any of paragraphs 17 to 26, wherein the multiblockpolyolefin is a liquid at 25° C.28. The process of any of paragraphs 13 to 27, wherein the Mn of themultiblock polyolefin is from about 300 to about 40,000 g/mol.29. The process of any of paragraphs 17 to 28, wherein the alkenemetathesis catalyst is represented by the Formula (I):

where:M is a Group 8 metal, preferably Ru or Os, preferably Ru;X and X¹ are, independently, any anionic ligand, preferably a halogen(preferably C₁), an alkoxide or a triflate, or X and X¹ may be joined toform a dianionic group and may form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms;L and L¹ are, independently, a neutral two electron donor, preferably aphosphine or a N-heterocyclic carbene, L and L¹ may be joined to form asingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms;L and X may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;L¹ and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;R and R¹ are, independently, hydrogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);R¹ and L¹ or X¹ may be joined to form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.30. The process of paragraph 29, wherein:

M is Ru or Os;

X and X¹ are, independently, a halogen, an alkoxide or a triflate, or Xand X¹ may be joined to form a dianionic group and may form single ringof up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L and L¹ are, independently, a phosphine or a N-heterocyclic carbene, Land L¹ may be joined to form a single ring of up to 30 non-hydrogenatoms or a multinuclear ring system, of up to 30 non-hydrogen atoms;L and X may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;L¹ and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;R and R¹ are, independently, hydrogen or a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl;R¹ and L¹ or X¹ may be joined to form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.31. The process of any of paragraphs 17 to 30 wherein the alkenemetathesis catalyst is one or more of:tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylene]ruthenium(II)dichloride,bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylideneruthenium(II)dichloride,1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride, and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II)chloride, benzylidene-bis(tricyclohexylphosphine)dichlororuthenium,benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium,dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II),(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium,1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-(2-pyridinyl)propylidene]ruthenium(II),[1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II), and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)bis(3-bromopyridine)ruthenium(II).

EXAMPLES Tests and Materials

Products were characterized by ¹H NMR, ¹³C NMR, and DSC as follows:

¹H NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹Hydrogen frequency of at least 400 MHz (forpurposes of the claims, 400 MHz shall be used). Data was recorded usinga maximum pulse width of 45°, 8 seconds between pulses and signalaveraging 120 transients. Spectral signals were integrated and thenumber of unsaturation types per 1000 carbons was calculated bymultiplying the different groups by 1000 and dividing the result by thetotal number of carbons.

¹³C NMR Spectroscopy

¹³C NMR data was collected at 120° C. in a 10 mm probe using a Varianspectrometer with a ¹Hydrogen frequency of at least 400 MHz (forpurposes of the claims, 400 MHz shall be used). A 90 degree pulse, anacquisition time adjusted to give a digital resolution between 0.1 and0.12 Hz, and at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating were employed during the entire acquisitionperiod. The spectra were acquired using time averaging to provide asignal to noise level adequate to measure the signals of interest.Samples were dissolved in tetrachloroethane-d₂ at concentrations between10 wt % to 15 wt % prior to being inserted into the spectrometer magnet.Prior to data analysis spectra were referenced by setting the chemicalshift of the (—CH₂—)_(n) signal where n>6 to 29.9 ppm. Internal sites ofunsaturation for quantitization were identified using the signals atabout 128 to about 132 ppm for internal unsaturation sites and at about114 and 139 ppm for reactive termini peaks in the ¹³C NMR spectrum. Forpurposes of the claims all ¹³C NMR spectra shall be acquired intetrachloroethane-d₂ at concentrations between 10 wt % to 15 wt % andall ¹³C NMR spectra are referenced to the chemical shift of the solventtetrachloroethane-d₂.

Polypropylene microstructure is determined by ¹³C NMR spectroscopy,including the concentration of isotactic and syndiotactic diads ([m] and[r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Thedesignation “m” or “r” describes the stereochemistry of pairs ofcontiguous propylene groups, “m” referring to meso and “r” to racemic.Samples are dissolved in d₂-1,1,2,2-tetrachloroethane, and spectrarecorded at 125° C. using a 400 MHz Varian NMR spectrometer having aproton frequency of 400 MHz. Polymer resonance peaks are referenced tommmm=21.8 ppm. Calculations involved in the characterization of polymersby NMR are described by F. A. Bovey in POLYMER CONFORMATION ANDCONFIGURATION (Academic Press, New York 1969) and J. Randall in POLYMERSEQUENCE DETERMINATION, ¹³C NMR METHOD (Academic Press, New York, 1977).

DSC

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning Calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature (approx 23° C.). Thesample is equilibrated at 25° C., then it is cooled at a cooling rate of10° C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., then heated at a heating rate of 10°C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified. For samples displaying multiple peaks,the melting point (or melting temperature) is defined to be the peakmelting temperature (i.e., associated with the largest endothermiccalorimetric response in that range of temperatures) from the DSCmelting trace.

All molecular weights are number average unless otherwise noted. Allmolecular weights are reported in g/mol.

The following abbreviations are used in the Examples:

Catalyst Zhan 1B is1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride (Strem Chemicals, catalog #44-0082) and Catalyst Neolyst M2is tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II)dichloride (Strem Chemicals, catalog #44-7777), aPP is atacticpolypropylene, iPP is isotactic polypropylene, EP is ethylene-propylenecopolymer, TCE is 1,1,2,2-tetrachloroethane, h is hours, min is minutes,M_(n) is the number average molecular weight as determined by ¹H NMRspectroscopy by comparison of integrals of the aliphatic region to theolefin region as determined using the protocol described in theExperimental section of WO 2009/155471.

Each of the specific examples described below uses a vinyl-containingreactant. 2-Methyl-1-undecene, 1-decene, 1-eicosene, and 1-octadecenewere purchased from Sigma Aldrich. The vinyl-terminated iPP,vinyl-terminated EP, and vinyl-terminated aPP were prepared as describedin WO 2009/155471.

EXAMPLES Example 1 Cross metathesis of vinyl-^(i)PP and vinyl-EP.Vinyl-terminated polypropylene (M_(n)=6900 g/mol, vinyl content 86%,T_(m) 79° C.) (7.52 g, 1.09 mmol), vinyl-terminated ethylene propylenecopolymer (M_(n)=2205 g/mol, vinyl content 94%, ethylene content approx.90 wt %) (2.40 g, 1.09 mmol) and xylenes (100 mL) were combined in a 250mL round-bottomed flask. The mixture was heated to 120° C. to form ahomogeneous solution. This was cooled to 50° C. and Zhan 1B (0.019 g,0.026 mmol) in dichloromethane (10 mL) was added. After 30 minutesnitrogen was slowly bubbled through the reaction mixture. After 2.25hours total reaction time the mixture was poured into stirring methanol(400 mL) and the resulting white solid was collected on a frit andwashed with methanol. The product was dried overnight under reducedpressure. Yield: 9.58 g. ¹H NMR spectroscopic data indicated that per1000 carbon atoms there were: 1.06 vinylenes, 0.50 vinyls, and 0.23vinylidenes. Assuming a thermodynamic mixture this gives a 37% yield ofthe heterodiblock product. Example 2 Cross Metathesis of2-methyl-1-undecene and 1-eicosene

1-Eicosene (1.77 g, 6.31 mmol), 2-methyl-1-undecene (1.06 g, 6.31 mmol)and Zhan 1B (0.0362 g, 0.0493 mmol) were combined in a vial. Thenpentane (5 mL) and dichloromethane (5 mL) were added to form ahomogeneous mixture that was heated on a metal block kept at 45° C.Additional pentane was added periodically as the mixture evaporated fora few hours. The mixture was kept at 39° C. overnight. At this time ¹HNMR spectroscopy indicated that the heterocoupled product had formed in50% yield (based on the starting mols of 2-methyl-1-decene), with theother alkene-containing species present in the mixture being9-octadecene and unreacted 2-methyl-1-undecene.

Example 3 Cross Metathesis of Vinyl-aPP and Vinyl-EP

Vinyl-terminated atactic polypropylene (M_(n)=884 g/mol) (1.72 g, 1.95mmol) and vinyl-terminated ethylene propylene copolymer (M_(n)=2205g/mol, vinyl content 94%, ethylene content approx. 90 wt %) (4.30 g,1.95 mmol) were combined and heated to 120° C. for 0.5 hours. Toluene (4mL) was added and the mixture was cooled to 90° C. Then while kept on ahot plate at 90° C., hexane (3 mL) was added followed by Neolyst M2(0.0123 g, 0.013 mmol) in toluene (1 mL). Gas evolution was observed.After 1 hour the hot mixture was poured slowly into stirring methanol(300 mL). A white, waxy solid was isolated and dried under reducedpressure. Yield: 5.2 g.

Example 4 Homometathesis of 1-decene

1-Decene (5.00 mL, 26.4 mmol) and hexane (10 mL) were heated to refluxon a heating block kept at 75° C. Then a toluene (2 mL) solution ofNeolyst M2 (0.0836 g, 0.0880 mmol) was added. Gas evolution wasobserved. After 18 hours the mixture was cooled to ambient temperature,and pentane (18 mL) was added. The mixture was passed through a plug ofneutral alumina. The volatiles were then removed under reduced pressureto afford a colorless oil of 9-octadecene. Yield: 3.12 g. Proton NMRdata shows greater than 95% conversion to homocoupled product.

NMR characterization of homocoupled product of 1-octadecene.1-Octadecene was homocoupled in a manner similar to that described inExample 4. The product isolated is predominantly the E-isomertetratriacont-17-ene. The full ¹H decoupled C NMR spectrum of thisproduct is shown in FIG. 1. The dominant signal at 130.8 ppm andrelatively weak signals at around 114 and 139 ppm indicate that thevinyl-containing starting material has been converted over 90% to thevinylene-containing product. Based on the 130.8 signal and the 32.8 ppmresonance it seems likely that only the E-isomer is present inconcentration to be observed. The assignments for all other signals areshown below which support the expected product structure.

TABLE 1 Observed ¹³C NMR data for (E)-tetrariacont-17-ene and expectedshifts for the unobserved Z isomer. E1-E2-E3-(E4)₁₂-E5-E6 =E6-E5-(E4)₁₂-E3-E2-E1 Carbon# E1 E2 E3 E4 E5 E6 E isomer 14.2 22.9 32.229 to 30 32.79 130.8 Z isomer 14.2 22.9 32.2 29 to 30 27.3* 130.0**Estimated shift based upon model compound. Only E isomer observed

To further substantiate the structure of the coupled product, intensitymeasurements were compared between the unsaturated and saturatedspectral regions. The intensity ratio of the areas shows that the numberof unsaturated to saturated carbons is 1:19.5. Since a ratio greaterthan 1:16 is hard to rationalize this result unfortunately calls intoquestion the quantitative nature of the data. This is surprising becauseacquisition conditions were chosen to insure the collection ofquantitative data. One way to evaluate this is to compare the intensityratio of the allylic methylene (32.8 ppm) to the olefinic (130.8 ppm)signal. The measured ratio of 1.04:1 is within experimental error of theexpected 1:1 ratio. This result indicates that the data is quantitativeand that conclusions based on signal intensities are justified.Therefore, the 1:19.5 unsaturated to saturated molar ratio may indicatethe presence of other components that are contributing to the area ofthe saturated region. In fact, close examination of the spectrum showsadditional signals which may be from residual starting material or othercomponents in the sample. Their presence can distort the signalrelationships from their expected values thus affecting quantitativeconclusions. Similarly, when the saturated chain end signals are used todetermine a carbon number that result is also greater than what would becalculated from the predicted structure. With both experimentallydetermined carbon numbers being greater than what it is for thepredicted structure it seems likely that other components are present inthe sample which are affecting intensity relationships.

NMR characterization of homocoupled vinyl-terminated aPP

Vinyl-terminated atactic polypropylene with Mn=421 was homocoupled in amanner similar to that described in Example 4. The ¹³C NMR of theproduct formed by the homo cross metathesis of an atactic low molecularweight (Mn=421) vinyl terminated propylene macromer is shown in FIG. 2.It is much more complex compared to the spectrum of(E)-tetratriacont-17-enethe homocoupled product of 1-octacene because ofthe many stereo configurations present in the atactic macromer. Thesedifferent structures create numerous signals that are incompletelyresolved. The lack of resonances at around 114 and 139 ppm and thepresence at 130 indicate essentially complete conversion of thevinyl-terminated aPP to vinylene-containing coupled product. Table 2accounts for this type of chemical shift dispersion by indicating rangesfor specific carbons in the product. These ranges include all carbons ofa specific type regardless of the stereochemical environment they arein.

TABLE 2 Observed ¹³C NMR data for (E)- and (Z)-aPP-aPP. 2′ 4′ 5′ 5′ 4′2′ 1-2-(3-4)_(n)-3-5-6-7 = 7-6-5-3-(4-3)_(n)-2-1 Carbon# 1 2 2′ 3 4 5 4′& 5′ 6 7 E-isomer 23.6 to 25.6 to 22.7 to 44.0 to 28.0 to 31.0 to 20.0to 40.0 to 130.2 to 24.0 26.2 23.2 49.0 29.0 32.0 22.0 42.0 130.6Z-isomer 23.6 to 25.6 to 22.7 to 44.0 to 28.0 to 31.0 to 20.0 to 35.5 to129.4 to 24.0 26.2 23.2 49.0 29.0 32.0 22.0 36.3 129.6

There is chemical shift evidence that both Z- and E-isomers have beensynthesized. As expected for both the unsaturated and allylic carbontypes, shifts for the E-isomer are shifted downfield (to the left)relative to the Z-configuration. From intensities of the signals theE-isomer is the preferred product with the Z- to E-ratio of 17:83. Theolefinic signal envelopes for the unsaturated carbons are also broadeneddue to the variable tacticity in the vicinity of the double bond.

As the case with the octadecene spectrum, the quantitative nature of thedata has been maintained. The intensity ratio of the unsaturated carbonsto the allylic methylene resonances are in agreement. Additionally, theZ- and E-allylic ratios are the same as the unsaturated carbon ratiosfurther supporting the assignments. A number average molecular weight of870 for the product was calculated by using the unsaturated and totalcarbon intensities. This value is a little higher than expected based onthe M_(n) of 421 for the vinylic starting material.

NMR Characterization of Products from the Cross-Metathesis of1-Octadecene and Vinyl-Terminated aPP.

1-Octadecene and vinyl terminated atactic polypropylene (Mn=421) werecross metathesized in a manner similar to the reaction described inExample 3. The cross metathesis of two or more alkene-containingpolyolefins will form mixture of homocoupled products (e.g., PO¹—PO¹)and heterocoupled products (e.g., PO¹-PO²). The heterocoupled diblockproducts will have a central vinylene group with asymmetric1,2-disubstitution. The structural asymmetry from having differentsubstituents on either side of the double bond should be detectable by CNMR. Table 3 contains the probable structure for the asymmetricheterocoupled product along with the observed carbon chemical shifts forthe signals that are different from the symmetric species. The C NMRspectrum is shown in FIG. 3. The lack of signals at around 114 and 139ppm and the strong resonances around 130 ppm indicate that thevinyl-containing reactants have been converted essentially completely topredominantly vinylene-containing products. Shifts for the other carbonsin the homocoupled products are included in Tables 1 and 2. Assignmentsof the olefinic signals were based upon chemical shift calculations andthe allylic resonances on model compounds.

TABLE 3 Distinguishing ¹³C NMR spectroscopic shifts for (E)- and(Z)-isomers of heterocoupled PE-PP products. 2′ 4′ 5′1-2-(3-4)_(n)-3-5-6-7 = E6-E5-(E4)₁₂-E3-E2-E1 Carbon# 7 (PP tail) E6 (PEtail) E5 (PE tail) E-isomer 128.4 to 129.3 132.0 to 132.4 32.84 Z-isomer129.4 to 129.6 130.9 to 131.5 27.7

FIG. 4 is a stacked plot of the saturated region of the heterocoupledmixture (bottom plot) and the two homocoupled products. The spectrum ofthe heterocoupled product contains all of the signals found in thehomocoupled data as well as new signals at 32.84 ppm (inset) and 27.7ppm. These resonances are from the E- and Z-allylic methylenes on theoctadecene arm in the heterocoupled product. The presence of the 27.7Z-allylic signal indicates that octadecene can form the Z-isomer when itis coupled with the polypropylene macromer. This contrasts to thehomocoupling of octadecene where only the E-isomer was observed. Thesignal of the allylic methylene on the polypropylene arm is not shiftedenough from the homopolypropylene product to be observed separately.

Due to the signal overlap of the saturated signals determining theproportion of each type of product in the mixture can not be made.However, the unsaturated region from the heterocoupled reaction mixturewill permit a composition calculation.

The average intensity of these heterocoupled signals were used tocalculate the composition of the heterocoupled PE-PP product mixtureafter it had been dissolved in warm hexanes and precipitated by theaddition of ethyl acetate. ¹³C NMR spectroscopic analysis of this solidindicated that its molar composition was 43% heterodiblock (31% Eisomer+12% Z isomer), 26% homo PP diblock (22% E isomer+4% Z isomer),and 31% homo PE diblock (only E isomer observed).

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related applications, and/or testing proceduresto the extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is NOT incorporated by reference herein. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

1. A composition comprising a multiblock polyolefin represented by theformula:PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X), or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen; PO and PO* are each, independently, polyolefins, provided thatat least one of PO and PO* are C₂₀ or greater, said multiblockpolyolefin having: 1) an internal unsaturation as shown by the ¹³C NMRpeak at between about 128 and about 132 ppm; and 2) an Mn ratio “Z”=0.1to 10, where Z is the Mn (as determined by ¹³C NMR) divided by Mn (asdetermined according to Gel Permeation Chromotography using polystyrenestandards).
 2. The composition of claim 1, wherein the multiblockpolyolefin has from 0.30(J) and 0.75(J) internal unsaturations per 1000carbons as determined by ¹H NMR spectroscopy, where J is the number ofreactive groups per 1000 carbons for the mixture of vinyl terminatedpolyolefins, that preferably become PO and PO*, before they are coupledby an alkene metathesis catalyst.
 3. The composition of claim 1, whereinPO* is PO.
 4. The composition of claim 1, wherein PO and PO* are each,independently, a substituted or unsubstituted hydrocarbyl group having 9to 4000 carbon atoms.
 5. The composition of claim 1, wherein thepolyolefin is a mixture of PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*,PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO andPO*—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*.
 6. The composition ofclaim 5, wherein the mixture comprises about 30% to about 70% ofPO—C(R¹¹)(R¹²)—C(R¹³)═C(R⁴)—C(R¹⁵)(R¹⁶)—PO*, about 1% to about 30% ofPO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO and about 1% to about 30%PO*—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*.
 7. The composition ofclaim 1, wherein each of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is a hydrogen.8. The composition of claim 1, wherein at least two of R¹¹, R¹², R¹³,R¹⁴, R¹⁵, and R¹⁶ are hydrogen atoms.
 9. The composition of claim 1,wherein at least four of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are hydrogenatoms.
 10. The composition of claim 1, wherein the multiblock polyolefinhas two peak melting temperatures (Tm) and the Tm's are different by atleast 5° C.
 11. The composition of claim 1, wherein the polyolefinPO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO* has a Mn of from 400 to120,000 g/mol.
 12. The composition of claim 1, wherein Z is 0.25 to 4.13. The composition of claim 1, wherein the polyolefinPO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO* has a Mn of 1,000 to 60,000g/mol.
 14. The composition of claim 1, wherein PO is a polypropylene ofan Mn of about 300 to about 20,000 g/mol.
 15. The composition of claim1, wherein PO is an ethylene/propylene copolymer having an Mn of about300 to about 20,000 g/mol.
 16. The composition of claim 1, wherein atleast one of PO or PO* is a substituted or unsubstituted hydrocarbylgroups having from about 2 to about 18 carbon atoms.
 17. A process toprepare a multiblock polyolefin represented by the formula (X):PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(R¹⁵)(R¹⁶)—PO*  (X), or isomers thereof,wherein R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶, are each independently asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group or ahydrogen; PO and PO* are each, independently, polyolefins, provided thatat least one of PO and PO* are C₂₀ or greater, said multiblockpolyolefin having: 1) an internal unsaturation as shown by the ¹³C NMRpeak at between about 128 and about 132 ppm; and 2) an Mn ratio “Z”=0.1to 10, where Z is the Mn (as determined by ¹³C NMR) divided by Mn (asdetermined according to Gel Permeation Chromotography using polystyrenestandards); and 3) optionally, from 0.3(J) and 0.75(J) internalunsaturations per 1000 carbons as determined by ¹H NMR spectroscopy,where J is the number of reactive groups per 1000 carbons for themixture of vinyl terminated polyolefins that become PO and PO*, beforethey are coupled by an alkene metathesis catalyst, comprising the stepof: contacting an alkene metathesis catalyst with two or more vinylterminated polyolefins each comprising more than 30% allyl chain ends(relative to total unsaturations).
 18. The process of claim 17, whereinat least one of the two or more vinyl terminated polyolefins comprisesabout 15 wt % to about 95 wt % ethylene and has more than 80% allylchain ends (relative to total unsaturations).
 19. The process of claim17, wherein at least one of the two or more vinyl terminated polyolefinscomprises about 30 wt % to about 95 wt % ethylene and has more than 70%allyl chain ends (relative to total unsaturations).
 20. The process ofclaim 17, wherein at least one of the two or more vinyl terminatedpolyolefins comprises about 30 wt % to about 95 wt % ethylene and hasmore than 90% allyl chain ends (relative to total unsaturations). 21.The process of claim 17, wherein at least one of the two or more vinylterminated polyolefins comprises about 15 wt % to about 95 wt %propylene and has more than 80% allyl chain ends (relative to totalunsaturations).
 22. The process of claim 17, wherein at least one of thetwo or more vinyl terminated polyolefins comprises about 30 wt % toabout 95 wt % propylene and has more than 70% allyl chain ends (relativeto total unsaturations).
 23. The process of claim 17, wherein at leastone of the two or more vinyl terminated polyolefins comprises about 30wt % to about 95 wt % propylene and has more than 90% allyl chain ends(relative to total unsaturations).
 24. The process of claim 17, whereinat least one of the two or more vinyl terminated polyolefins comprisesabout 15 wt % to about 95 wt % ethylene-propylene copolymer and has morethan 80% allyl chain ends (relative to total unsaturations).
 25. Theprocess of claim 17, wherein at least one of the two or more vinylterminated polyolefins comprises about 30 wt % to about 95 wt %ethylene-propylene copolymer and has more than 70% allyl chain ends(relative to total unsaturations).
 26. The process of claim 17, whereinat least one of the two or more vinyl terminated polyolefins comprisesabout 30 wt % to about 95 wt % ethylene-propylene copolymer and has morethan 90% allyl chain ends (relative to total unsaturations).
 27. Theprocess of claim 17, wherein the multiblock polyolefin is a liquid at25° C.
 28. The process of claim 17, wherein the Mn of the multiblockpolyolefin is from about 300 to about 40,000 g/mol.
 29. The process ofclaim 17, wherein the alkene metathesis catalyst is represented by theFormula (I):

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may forma single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms; L and L¹ are neutral two electrondonors, L and L¹ may be joined to form a single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; L and X may be joined to form a bidentatemonoanionic group and may form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; L¹and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms; R and R¹ are, independently,hydrogen or C₁ to C₃₀ substituted or unsubstituted hydrocarbyl; R¹ andL¹ or X¹ may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; 30.The process of claim 29, wherein: M is Ru or Os; X and X¹ are,independently, a halogen, an alkoxide or a triflate, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; L and L¹ are, independently, a phosphine or aN-heterocyclic carbene, L and L¹ may be joined to form a single ring ofup to 30 non-hydrogen atoms or a multinuclear ring system, of up to 30non-hydrogen atoms; L and X may be joined to form a multidentatemonoanionic group and may form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; L¹and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms; R and R¹ are, independently,hydrogen or a C₁ to C₃₀ substituted or unsubstituted alkyl or asubstituted or unsubstituted C₄ to C₃₀ aryl; R¹ and L¹ or X¹ may bejoined to form single ring of up to 30 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms; and R and L orX may be joined to form single ring of up to 30 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms.
 31. The processof claim 17, wherein the alkene metathesis catalyst is one or more of:tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylene]ruthenium(II)dichloride,bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylideneruthenium(II)dichloride,1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride, and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II)chloride, benzylidene-bis(tricyclohexylphosphine)dichlororuthenium,benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium,dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II),(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium,1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-(2-pyridinyl)propylidene]ruthenium(II),[1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II), and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)bis(3-bromopyridine)ruthenium(II).32. The multiblock polyolefin of claim 1 wherein the multiblockpolyolefin has 0.10 to 35 internal unsaturations per 1,000 carbon atomsas determined by ¹³C NMR).